Theoretical study of coupling mechanisms between oxygen diffusion, chemical reaction, mechanical stresses in a solid-gas reactive system

International Nuclear Information System (INIS)

Creton, N.; Optasanu, V.; Montesin, T.; Garruchet, S.

2008-01-01

This paper offers a study of oxygen dissolution into a solid, and its consequences on the mechanical behaviour of the material. In fact, mechanical strains strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO 2 compound near the internal interface is consistent with some oxidation mechanisms of oxidation experimentally observed. More generally, this work will be extended to the simulation to an oxide layer growth on a metallic substrate. (authors)

Experimental evidence of hydrogen–oxygen decoupled diffusion into BaZr0.6Ce0.25Y0.15O3−δ

International Nuclear Information System (INIS)

Lim, D.-K.; Im, H.-N.; Jeon, S.-Y.; Park, J.-Y.; Song, S.-J.

2013-01-01

The electrical properties of BaZr 0.6 Ce 0.25 Y 0.15 O 3−δ (BZCY) were studied as a function of both oxygen partial pressure (-2.65⩽log(P O 2 atm -1 )⩽-0.62) and water vapor activity (-3.33⩽log(P H 2 O atm -1 ⩽-1.3)) in the temperature range of 973–1073 K. The total conductivity slightly increased in reducing atmospheres with increasing water vapor activity because of the relative contribution to the total conductivity by the redox reaction at the given thermodynamic conditions. The partial conductivities of protons, holes and oxygen vacancies were successfully calculated, and the activation energy determined for proton transport was 0.3 ± 0.1 eV. The chemical diffusivity of oxygen at a fixed water vapor activity, D ∼ vO , could only be evaluated from Fick’s second law during oxidation and reduction at the fixed water vapor activity. However, twofold nonmonotonic conductivity relaxation behaviors were clearly confirmed in the temperature range investigated during hydration/dehydration. If P O 2 represents the fixed oxygen partial pressure, D ∼ iH is the hydrogen chemical diffusivity at P O 2 and D ∼ vH is the oxygen chemical diffusivity at P O 2 , it was observed that D ∼ iH >D ∼ vH at all experimental conditions, suggesting that the hydrogen chemical diffusion is always faster than oxygen on hydration/dehydration in the temperature range studied

Anisotropic Oxygen Ion Diffusion in Layered PrBaCo 2 O 5+δ

KAUST Repository

Burriel, Mónica

2012-02-14

Oxygen diffusion and surface exchange coefficients have been measured on polycrystalline samples of the double perovskite oxide PrBaCo 2O 5+δ by the isotope exchange depth profile method, using a time-of-flight SIMS instrument. The measured diffusion coefficients show an activation energy of 1.02 eV, as compared to 0.89 eV for the surface exchange coefficients in the temperature range from 300 to 670 °C. Inhomogeneity was observed in the distribution of the oxygen-18 isotopic fraction from grain to grain in the ceramic samples, which was attributed to anisotropy in the diffusion and exchange of oxygen. By the use of a novel combination of electron back scattered diffraction measurements, time-of-flight, and focused ion beam SIMS, this anisotropy was confirmed by in-depth analysis of single grains of known orientation in a ceramic sample exchanged at 300 °C. Diffusion was shown to be faster in a grain oriented with the surface normal close to 100 and 010 (ab-plane oriented) than a grain with a surface normal close to 001 (c-axis oriented). The magnitude of this anisotropy is estimated to be close to a factor of 4, but this is only a lower bound due to experimental limitations. These findings are consistent with recent molecular dynamic simulations of this material where anisotropy in the oxygen transport was predicted. © 2012 American Chemical Society.

Anisotropic Oxygen Ion Diffusion in Layered PrBaCo 2 O 5+δ

KAUST Repository

Burriel, Mó nica; Peñ a-Martí nez, Juan; Chater, Richard J.; Fearn, Sarah; Berenov, Andrey V.; Skinner, Stephen J.; Kilner, John A.

2012-01-01

Oxygen diffusion and surface exchange coefficients have been measured on polycrystalline samples of the double perovskite oxide PrBaCo 2O 5+δ by the isotope exchange depth profile method, using a time-of-flight SIMS instrument. The measured diffusion coefficients show an activation energy of 1.02 eV, as compared to 0.89 eV for the surface exchange coefficients in the temperature range from 300 to 670 °C. Inhomogeneity was observed in the distribution of the oxygen-18 isotopic fraction from grain to grain in the ceramic samples, which was attributed to anisotropy in the diffusion and exchange of oxygen. By the use of a novel combination of electron back scattered diffraction measurements, time-of-flight, and focused ion beam SIMS, this anisotropy was confirmed by in-depth analysis of single grains of known orientation in a ceramic sample exchanged at 300 °C. Diffusion was shown to be faster in a grain oriented with the surface normal close to 100 and 010 (ab-plane oriented) than a grain with a surface normal close to 001 (c-axis oriented). The magnitude of this anisotropy is estimated to be close to a factor of 4, but this is only a lower bound due to experimental limitations. These findings are consistent with recent molecular dynamic simulations of this material where anisotropy in the oxygen transport was predicted. © 2012 American Chemical Society.

SIMS study of oxygen diffusion in monoclinic HfO2

Science.gov (United States)

Mueller, Michael P.; De Souza, Roger A.

2018-01-01

The diffusion of oxygen in dense ceramics of monoclinic HfO2 was studied by means of (18O/16O) isotope exchange annealing and subsequent determination of isotope depth profiles by Secondary Ion Mass Spectrometry. Anneals were performed in the temperature range of 573 ≤T /K ≤ 973 at an oxygen partial pressure of p O2=200 mbar . All measured isotope profiles exhibited two features: the first feature, closer to the surface, was attributed mainly to slow oxygen diffusion in an impurity silicate phase; the second feature, deeper in the sample, was attributed to oxygen diffusion in bulk monoclinic HfO2 . The activation enthalpy of oxygen tracer diffusion in bulk HfO2 was found to be ΔHD∗≈0.5 eV .

Diffusion of oxygen in niobium during bake-out

CERN Document Server

Calatroni, Sergio; Ruzinov, V

2001-01-01

Bake-outs at temperatures between 100 C and 150 C for a duration up to two days have become customary for optimising the performance of bulk niobium cavities. This treatment results in the diffusion of oxygen, originating from the surface oxide, into the niobium. The theoretical oxygen profile has been simulated using the diffusion equations, and compared with some experimental results.

Diffusion of oxygen in niobium during bake-out

International Nuclear Information System (INIS)

Benvenuti, C.; Calatroni, S.; Ruzinov, V.

2003-01-01

Bake-outs at temperatures between 100 degC and 150 degC for duration up to two days have become customary for optimising the performance of bulk niobium cavities. This treatment results in the diffusion of oxygen, originating from the surface oxide, into the niobium. The theoretical oxygen profile has been simulated using the diffusion equations, and compared with some experimental results. (author)

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Sathiyanarayanan, Rajesh, E-mail: rajessat@in.ibm.com, E-mail: rajesh.sathiyanarayanan@gmail.com; Pandey, R. K.; Murali, K. V. R. M. [IBM Semiconductor Research and Development Center, Bangalore 560045 (India)

2015-01-21

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switching mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

Science.gov (United States)

Good, Brian

2011-01-01

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Determination of oxygen effective diffusivity in porous gas diffusion layer using a three-dimensional pore network model

International Nuclear Information System (INIS)

Wu Rui; Zhu Xun; Liao Qiang; Wang Hong; Ding Yudong; Li Jun; Ye Dingding

2010-01-01

In proton exchange membrane fuel cell (PEMFC) models, oxygen effective diffusivity is the most important parameter to characterize the oxygen transport in the gas diffusion layer (GDL). However, its determination is a challenge due to its complex dependency on GDL structure. In the present study, a three-dimensional network consisting of spherical pores and cylindrical throats is developed and used to investigate the effects of GDL structural parameters on oxygen effective diffusivity under the condition with/without water invasion process. Oxygen transport in the throat is described by Fick's law and water invasion process in the network is simulated using the invasion percolation with trapping algorithm. The simulation results reveal that oxygen effective diffusivity is slightly affected by network size but increases with decreasing the network heterogeneity and with increasing the pore connectivity. Impacts of network anisotropy on oxygen transport are also investigated in this paper. The anisotropic network is constructed by constricting the throats in the through-plane direction with a constriction factor. It is found that water invasion has a more severe negative influence on oxygen transport in an anisotropic network. Finally, two new correlations are introduced to determine the oxygen effective diffusivity for the Toray carbon paper GDLs.

Oxygen and nitrogen diffusion in coal-molecular sieve

International Nuclear Information System (INIS)

Stefanescu, Doina Maria

1996-01-01

Recently, the air separation process based on selective adsorption of carbon-molecular sieves has been developed strongly. The separation is based on the system kinematics and depends on the oxygen diffusion in adsorber micropores. The oxygen is preferentially adsorbed and in given conditions it is possible to obtain nitrogen of high purity. Recent theoretical and experimental studies concerning the production of nitrogen by PSA process have shown that the obtained performances can not be described by a constant diffusion model. The paper present the 'dual' model assumed for O 2 and N 2 diffusion through molecular sieve as well as the experimental data obtained in the adsorption study on carbon material produced at ICIS to determine the diffusivity values in micropores

Germanium diffusion with vapor-phase GeAs and oxygen co-incorporation in GaAs

Science.gov (United States)

Wang, Wei-Fu; Cheng, Kai-Yuan; Hsieh, Kuang-Chien

2018-01-01

Vapor-phase germanium diffusion has been demonstrated in Zn-doped and semi-insulating GaAs in sealed ampoules with GeAs powders and excess arsenic. Secondary-ion-mass spectroscopy (SIMS) profiles indicate the presence of unintentional co-incorporation of oxygen in high densities (>1017/cm3) along with diffused germanium donors whose concentration (>>1018/cm3) determined by electro-chemical capacitance-voltage (ECV) profiler shows significant compensation near the surface. The source of oxygen mainly originates from the GeAs powder which contains Ge-O surface oxides. Variable-temperature photoluminescence (PL) shows that in GeAs-diffused samples, a broad peak ranging from 0.86-1.38 eV with the peak position around 1.1 eV predominates at low temperatures while the near band-edge luminescence quenches. The broad band is attributed to the GeGa-VGa self-activated (SA) centers possibly associated with nearby oxygen-related defect complex, and its luminescence persists up to 400 K. The configurational-coordinate modeling finds that the SA defect complex has a thermal activation energy of 150-180 meV and a vibrational energy 26.8 meV. The presence of oxygen does not much affect the SA emission intensity but may have influenced the peak position, vibration frequency and activation energy as compared to other common donor-VGa defects in GaAs.

Germanium diffusion with vapor-phase GeAs and oxygen co-incorporation in GaAs

Directory of Open Access Journals (Sweden)

Wei-Fu Wang

2018-01-01

Full Text Available Vapor-phase germanium diffusion has been demonstrated in Zn-doped and semi-insulating GaAs in sealed ampoules with GeAs powders and excess arsenic. Secondary-ion-mass spectroscopy (SIMS profiles indicate the presence of unintentional co-incorporation of oxygen in high densities (>1017/cm3 along with diffused germanium donors whose concentration (>>1018/cm3 determined by electro-chemical capacitance-voltage (ECV profiler shows significant compensation near the surface. The source of oxygen mainly originates from the GeAs powder which contains Ge-O surface oxides. Variable-temperature photoluminescence (PL shows that in GeAs-diffused samples, a broad peak ranging from 0.86-1.38 eV with the peak position around 1.1 eV predominates at low temperatures while the near band-edge luminescence quenches. The broad band is attributed to the GeGa-VGa self-activated (SA centers possibly associated with nearby oxygen-related defect complex, and its luminescence persists up to 400 K. The configurational-coordinate modeling finds that the SA defect complex has a thermal activation energy of 150-180 meV and a vibrational energy 26.8 meV. The presence of oxygen does not much affect the SA emission intensity but may have influenced the peak position, vibration frequency and activation energy as compared to other common donor-VGa defects in GaAs.

REVIEW ARTICLE: Oxygen diffusion and precipitation in Czochralski silicon

Science.gov (United States)

Newman, R. C.

2000-06-01

The objective of this article is to review our understanding of the properties of oxygen impurities in Czochralski silicon that is used to manufacture integrated circuits (ICs). These atoms, present at a concentration of ~1018 cm-3, occupy bond-centred sites (Oi) in as-grown Si and the jump rate between adjacent sites defines `normal' diffusion for the temperature range 1325 - 330 °C. Anneals at high temperatures lead to the formation of amorphous SiO2 precipitates that act as traps for fast diffusing metallic contaminants, such as Fe and Cu, that may be inadvertently introduced at levels as low as 1011 cm-3. Without this `gettering', there may be severe degradation of fabricated ICs. To accommodate the local volume increase during oxygen precipitation, there is parallel generation of self-interstitials that diffuse away and form lattice defects. High temperature (T > 700 °C) anneals are now well understood. Details of lower temperature processes are still a matter of debate: measurements of oxygen diffusion into or out of the Si surface and Oi atom aggregation have implied enhanced diffusion that has variously been attributed to interactions of Oi atoms with lattice vacancies, self-interstitials, metallic elements, carbon, hydrogen impurities etc. There is strong evidence for oxygen-hydrogen interactions at T continue to decrease as the size of future device features decreases below the lower end of the sub-micron range, currently close to 0.18 µm.

Solubility and diffusion coefficient of oxygen in silicon

International Nuclear Information System (INIS)

Itoh, Yoshiko; Nozaki, Tadashi

1985-01-01

The solubility and diffusion coefficient of oxygen in silicon between 1000 0 C and 1375 0 C were examined by charged particle activation analysis with the 16 O( 3 He,p) 18 F reaction, in which oxygen was activated with an equal probability over the depth of up to 250μm by a specially devised apparatus. Silicon wafers of known histories were heated in oxygen or argon for 12 to 473 hours, and the resultant oxygen depth profiles were determined by the activation, subsequent stepwise etching and 18 F activity measurement. The solubility thus obtained is given as 9.3 x 10 21 exp[-27.6kcal mol -1 /RT] at.cm -3 ; the diffusion coefficient has been found to be approximated as 3.2 exp[-67.1kcal mol -1 /RT] cm 2 s -1 over 1150 0 C, under which the apparent activation energy seems to decrease with decrease of temperature. (author)

Oxygen diffusion model of the mixed (U,Pu)O{sub 2±x}: Assessment and application

Energy Technology Data Exchange (ETDEWEB)

Moore, Emily, E-mail: eemevans@gmail.com [Den-Service de la Corrosion et du Comportement des Matériaux dans leur Environment (SCCME), CEA, Université Paris-Saclay, F-91191 Gif-sur-Yvette, Cedex (France); Guéneau, Christine [Den-Service de la Corrosion et du Comportement des Matériaux dans leur Environment (SCCME), CEA, Université Paris-Saclay, F-91191 Gif-sur-Yvette, Cedex (France); Crocombette, Jean-Paul [Den-Service de Recherche de Métallurgie Physique (SRMP), CEA, Université Paris-Saclay, F-91191 Gif-sur-Yvette, Cedex (France)

2017-03-15

The uranium-plutonium (U,Pu)O{sub 2±x} mixed oxide (MOX) is used as a nuclear fuel in some light water reactors and considered for future reactor generations. To gain insight into fuel restructuring, which occurs during the fuel lifetime as well as possible accident scenarios understanding of the thermodynamic and kinetic behavior is crucial. A comprehensive evaluation of thermo-kinetic properties is incorporated in a computational CALPHAD type model. The present DICTRA based model describes oxygen diffusion across the whole range of plutonium, uranium and oxygen compositions and temperatures by incorporating vacancy and interstitial migration pathways for oxygen. The self and chemical diffusion coefficients are assessed for the binary UO{sub 2±x} and PuO{sub 2−x} systems and the description is extended to the ternary mixed oxide (U,Pu)O{sub 2±x} by extrapolation. A simulation to validate the applicability of this model is considered.

Stress dependence of oxygen diffusion in ZrO2 film

International Nuclear Information System (INIS)

Yamamoto, Yasunori; Morishita, Kazunori; Iwakiri, Hirotomo; Kaneta, Yasunori

2013-01-01

First principles calculations were performed to evaluate the effect of stress on the diffusion process of oxygen atoms in monoclinic and tetragonal ZrO 2 . The formation and migration energies of an oxygen vacancy were obtained as a function of applied stress. Our results show that the formation and migration energies increase when the compressive stress is applied, which causes a reduction in the diffusion coefficient of an oxygen atom in ZrO 2 . This may explain the experimental observation that the oxide film grows in proportion to the cubic root of time

Oxygen diffusion in nanocrystalline yttria-stabilized zirconia: the effect of grain boundaries.

Science.gov (United States)

De Souza, Roger A; Pietrowski, Martha J; Anselmi-Tamburini, Umberto; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

2008-04-21

The transport of oxygen in dense samples of yttria-stabilized zirconia (YSZ), of average grain size d approximately 50 nm, has been studied by means of 18O/16O exchange annealing and secondary ion mass spectrometry (SIMS). Oxygen diffusion coefficients (D*) and oxygen surface exchange coefficients (k*) were measured for temperatures 673oxygen partial pressure of 900 mbar. No evidence is found for fast diffusion along grain boundaries. Rather, the analysis indicates that grain boundaries hinder oxygen transport.

Oxygen concentration diffusion analysis of lead-bismuth-cooled, natural-circulation reactor

International Nuclear Information System (INIS)

Ito, Kei; Sakai, Takaaki

2001-11-01

The feasibility study on fast breeder reactors in Japan has been conducted at JNC and related organizations. The Phase-I study has finished in March, 2001. During the Phase-I activity, lead-bismuth eutectic coolant has been selected as one of the possible coolant options and a medium-scale plant, cooled by a lead-bismuth natural circulation flow was studied. On the other side, it is known that lead-bismuth eutectic has a problem of structural material corrosiveness. It was found that oxygen concentration control in the eutectic plays an important role on the corrosion protection. In this report, we have developed a concentration diffusion analysis code (COCOA: COncentration COntrol Analysis code) in order to carry out the oxygen concentration control analysis. This code solves a two-dimensional concentration diffusion equation by the finite differential method. It is possible to simulate reaction of oxygen and hydrogen by the code. We verified the basic performance of the code and carried out oxygen concentration diffusion analysis for the case of an oxygen increase by a refueling process in the natural circulation reactor. In addition, characteristics of the oxygen control system was discussed for a different type of the control system as well. It is concluded that the COCOA code can simulate diffusion of oxygen concentration in the reactor. By the analysis of a natural circulation medium-scale reactor, we make clear that the ON-OFF control and PID control can well control oxygen concentration by choosing an appropriate concentration measurement point. In addition, even when a trouble occurs in the oxygen emission or hydrogen emission system, it observes that control characteristic drops away. It is still possible, however, to control oxygen concentration in such case. (author)

Zirconium metal-water oxidation kinetics. III. Oxygen diffusion in oxide and alpha Zircaloy phases

International Nuclear Information System (INIS)

Pawel, R.E.

1976-10-01

The reaction of Zircaloy in steam at elevated temperature involves the growth of discrete layers of oxide and oxygen-rich alpha Zircaloy from the parent beta phase. The multiphase, moving boundary diffusion problem involved is encountered in a number of important reaction schemes in addition to that of Zircaloy-oxygen and can be completely (albeitly ideally) characterized through an appropriate model in terms of oxygen diffusion coefficients and equilibrium concentrations for the various phases. Conversely, kinetic data for phase growth and total oxygen consumption rates can be used to compute diffusion coefficients. Equations are developed that express the oxygen diffusion coefficients in the oxide and alpha phases in terms of the reaction rate constants and equilibrium solubility values. These equations were applied to recent experimental kinetic data on the steam oxidation of Zircaloy-4 to determine the effective oxygen diffusion coefficients in these phases over the temperature range 1000--1500 0 C

Oxygen diffusion in high-Tc superconductors

International Nuclear Information System (INIS)

Rothman, S.J.; Routbort, J.L.

1992-07-01

The cuprate superconductors are fascinating not only because of their technical promise, but also because of their structures, especially the anisotropy of the crystal lattice. There are some structural similarities among these compounds, but also significant differences. Measurements of the oxygen tracer diffusion coefficients have been carried out as a function of temperature, oxygen partial pressure, crystal orientation, and doping in the La-Sr-Cu-0, Y-Ba-Cu-0, and Bi-Sr-Ca-Cu-0 systems. These measurements have revealed a variety of defect mechanisms operating in these compounds; the exact nature of the mechanism depends on the details of the structure

Structural characterisation of oxygen diffusion hardened alpha-tantalum PVD-coatings on titanium.

Science.gov (United States)

Hertl, C; Koll, L; Schmitz, T; Werner, E; Gbureck, U

2014-08-01

Titanium substrates were coated with tantalum layers of 5 μm thickness using physical vapour deposition (PVD). The tantalum layers showed a (110)-preferred orientation. The coated samples were hardened by oxygen diffusion. Using X-ray diffraction the crystallographic structure of the tantalum coatings was characterised, comparing untreated and diffusion hardened specimen conditions. Oxygen depth profiles were determined by glow discharge spectrometry. The hardening effect of the heat treatment was examined by Vickers microhardness testing. The increase of surface hardness caused by oxygen diffusion was at least 50%. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxygen potentials, oxygen diffusion coefficients and defect equilibria of nonstoichiometric (U,Pu)O{sub 2±x}

Energy Technology Data Exchange (ETDEWEB)

Kato, Masato, E-mail: kato.masato@jaea.go.jp [Fukushima Fuels and Materials Department, Japan Atomic Energy Agency, 4002 Narita-chou, O-arai machi, Ibaraki 311-1919 (Japan); Fast Reactor Fuel Cycle Technology Development Division, Japan Atomic Energy Agency, 4-33 Muramatsu Tokai-mura, Ibaraki 319-1194 (Japan); Watanabe, Masashi [Fukushima Fuels and Materials Department, Japan Atomic Energy Agency, 4002 Narita-chou, O-arai machi, Ibaraki 311-1919 (Japan); Fast Reactor Fuel Cycle Technology Development Division, Japan Atomic Energy Agency, 4-33 Muramatsu Tokai-mura, Ibaraki 319-1194 (Japan); Matsumoto, Taku; Hirooka, Shun; Akashi, Masatoshi [Fast Reactor Fuel Cycle Technology Development Division, Japan Atomic Energy Agency, 4-33 Muramatsu Tokai-mura, Ibaraki 319-1194 (Japan)

2017-04-15

Oxygen potential of (U,Pu)O{sub 2±x} was evaluated based on defect chemistry using an updated experimental data set. The relationship between oxygen partial pressure and deviation x in (U,Pu)O{sub 2±x} was analyzed, and equilibrium constants of defect formation were determined as functions of Pu content and temperature. Brouwer's diagrams were constructed using the determined equilibrium constants, and a relational equation to determine O/M ratio was derived as functions of O/M ratio, Pu content and temperature. In addition, relationship between oxygen potential and oxygen diffusion coefficients were described. - Highlights: •Brouwer’s diagrams for (U,Pu)O2 were constructed using the updated oxygen potential experimental data set. •Equilibrium constants of defect formation were determined as functions of Pu content and temperature. •Oxygen potential, oxygen diffusion coefficients, point defect concentration were described as functions of O/M ratio, Pu content and temperature.

Stress dependence of oxygen diffusion in ZrO{sub 2} film

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Yasunori, E-mail: yasu-yamamoto@iae.kyoto-u.ac.jp [Graduate School of Energy Science, Kyoto University, Uji, Kyoto 611-0011 (Japan); Morishita, Kazunori [Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011 (Japan); Iwakiri, Hirotomo [Faculty of Education, University of the Ryukyus, Nakagami-gun, Okinawa 903-0213 (Japan); Kaneta, Yasunori [Akita National College of Technology, Akita, Akita 011-8511 (Japan)

2013-05-15

First principles calculations were performed to evaluate the effect of stress on the diffusion process of oxygen atoms in monoclinic and tetragonal ZrO{sub 2}. The formation and migration energies of an oxygen vacancy were obtained as a function of applied stress. Our results show that the formation and migration energies increase when the compressive stress is applied, which causes a reduction in the diffusion coefficient of an oxygen atom in ZrO{sub 2}. This may explain the experimental observation that the oxide film grows in proportion to the cubic root of time.

Fundamental data: Solubility of nickel and oxygen and diffusivity of iron and oxygen in molten LBE

International Nuclear Information System (INIS)

Abella, J.; Verdaguer, A.; Colominas, S.; Ginestar, K.; Martinelli, L.

2011-01-01

Experiments for determining nickel solubility limit and iron diffusion coefficient are presented and their results are discussed. Nickel solubility limit is determined by two methods: ex situ by solid sampling followed by ICP-AES analysis and in situ by Laser Induced Breakdown Spectroscopy and their results are compared. The iron diffusion coefficient is obtained using the technique of rotating specimen dissolution. Also a method to determine the oxygen solubility and diffusivity in LBE is developed and results at 460, 500 and 540 deg. C are presented. It is based on the following electrochemical cell: O 2 (reference mixture), Pt //YSZ//O 2 (LBE) which can work as an oxygen sensor or as a coulometric pump.

Laminar oxy-fuel diffusion flame supported by an oxygen-permeable-ion-transport membrane

KAUST Repository

Hong, Jongsup

2013-03-01

A numerical model with detailed gas-phase chemistry and transport was used to predict homogeneous fuel conversion processes and to capture the important features (e.g., the location, temperature, thickness and structure of a flame) of laminar oxy-fuel diffusion flames stabilized on the sweep side of an oxygen permeable ion transport membrane (ITM). We assume that the membrane surface is not catalytic to hydrocarbon or syngas oxidation. It has been demonstrated that an ITM can be used for hydrocarbon conversion with enhanced reaction selectivity such as oxy-fuel combustion for carbon capture technologies and syngas production. Within an ITM unit, the oxidizer flow rate, i.e., the oxygen permeation flux, is not a pre-determined quantity, since it depends on the oxygen partial pressures on the feed and sweep sides and the membrane temperature. Instead, it is influenced by the oxidation reactions that are also dependent on the oxygen permeation rate, the initial conditions of the sweep gas, i.e., the fuel concentration, flow rate and temperature, and the diluent. In oxy-fuel combustion applications, the sweep side is fuel-diluted with CO2, and the entire unit is preheated to achieve a high oxygen permeation flux. This study focuses on the flame structure under these conditions and specifically on the chemical effect of CO2 dilution. Results show that, when the fuel diluent is CO2, a diffusion flame with a lower temperature and a larger thickness is established in the vicinity of the membrane, in comparison with the case in which N2 is used as a diluent. Enhanced OH-driven reactions and suppressed H radical chemistry result in the formation of products with larger CO and H2O and smaller H2 concentrations. Moreover, radical concentrations are reduced due to the high CO2 fraction in the sweep gas. CO2 dilution reduces CH3 formation and slows down the formation of soot precursors, C2H2 and C2H4. The flame location impacts the species diffusion and heat transfer from the

Species specificity of resistance to oxygen diffusion in thin cuticular membranes from amphibious plants

DEFF Research Database (Denmark)

Frost-Christensen, Henning; Jørgensen, Lise Bolt; Floto, Franz

2003-01-01

oxygen, diffusion, cuticula, amphibious plants, Hygrophila, Berula, Lobelia, Mentha, Potamogeton, Veronica, aquatic plants, submerged plants......oxygen, diffusion, cuticula, amphibious plants, Hygrophila, Berula, Lobelia, Mentha, Potamogeton, Veronica, aquatic plants, submerged plants...

Irradiation of cells by single and double pulses of high intensity radiation: oxygen sensitization and diffusion kinetics

International Nuclear Information System (INIS)

Epp, E.R.; Ling, C.C.; Weiss, H.

1976-01-01

This paper discusses advances made on both experimental and theoretical approaches involving single and double pulses of high intensity ionizing radiation delivered to cultured bacterial and mammalian cells where the effect of oxygen is concerned. Information gained on the lifetime of oxygen-sensitive species suspected to be produced in critical molecules in irradiated cells and perhaps intimately related to the still unknown mechanisms of oxygen sensitization is described. The diffusion characteristics of oxygen at the cellular level obtained from experimental data are discussed. Current knowledge on intracellular radiolytic oxygen depletion is also presented. Future work on the use of high intensity pulsed radiation as a tool in cellular radiobiological research is outlined. It is expected that obtaining knowledge of the time available for damaged molecules to enter into chemical reactions may lead to insights into the mechanisms of radiation injury in cells, such as those involved in the oxygen effect. (Auth.)

Excess oxygen limited diffusion and precipitation of iron in amorphous silicon dioxide

Science.gov (United States)

Leveneur, J.; Langlois, M.; Kennedy, J.; Metson, James B.

2017-10-01

In micro- and nano- electronic device fabrication, and particularly 3D designs, the diffusion of a metal into sublayers during annealing needs to be minimized as it is usually detrimental to device performance. Diffusion also causes the formation and growth of nanoprecipitates in solid matrices. In this paper, the diffusion behavior of low energy, low fluence, ion implanted iron into a thermally grown silicon oxide layer on silicon is investigated. Different ion beam analysis and imaging techniques were used. Magnetization measurements were also undertaken to provide evidence of nanocrystalline ordering. While standard vacuum furnace annealing and electron beam annealing lead to fast diffusion of the implanted species towards the Si/SiO2 interface, we show that furnace annealing in an oxygen rich atmosphere prevents the diffusion of iron that, in turn, limits the growth of the nanoparticles. The diffusion and particle growth is also greatly reduced when oxygen atoms are implanted in the SiO2 prior to Fe implantation, effectively acting as a diffusion barrier. The excess oxygen is hypothesized to trap Fe atoms and reduce their mean free path during the diffusion. Monte-Carlo simulations of the diffusion process which consider the random walk of Fe, Fick's diffusion of O atoms, Fe precipitation, and desorption of the SiO2 layer under the electron beam annealing were performed. Simulation results for the three preparation conditions are found in good agreement with the experimental data.

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

NARCIS (Netherlands)

Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

2015-01-01

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO2 films were found to show Arrhenius behaviour. However, a

Effect of chemical redox on Gd-doped ceria mass diffusion

DEFF Research Database (Denmark)

Ni, De Wei; de Florio, D.Z.; Marani, Debora

2015-01-01

The valence and size of cations influence mass diffusion and oxygen defects in ceria. Here we show that reduction of Ce4+ to Ce3+, at high temperatures and low oxygen activity, activates fast diffusion mechanisms which depend on the aliovalent cation concentration. As a result, polycrystalline so...... solid solutions with enhanced electrochemical properties are formed....

Modeling the oxygen diffusion of nanocomposite-based food packaging films.

Science.gov (United States)

Bhunia, Kanishka; Dhawan, Sumeet; Sablani, Shyam S

2012-07-01

Polymer-layered silicate nanocomposites have been shown to improve the gas barrier properties of food packaging polymers. This study developed a computer simulation model using the commercial software, COMSOL Multiphysics to analyze changes in oxygen barrier properties in terms of relative diffusivity, as influenced by configuration and structural parameters that include volume fraction (φ), aspect ratio (α), intercalation width (W), and orientation angle (θ) of nanoparticles. The simulation was performed at different φ (1%, 3%, 5%, and 7%), α (50, 100, 500, and 1000), and W (1, 3, 5, and 7 nm). The θ value was varied from 0° to 85°. Results show that diffusivity decreases with increasing volume fraction, but beyond φ = 5% and α = 500, diffusivity remained almost constant at W values of 1 and 3 nm. Higher relative diffusivity coincided with increasing W and decreasing α value for the same volume fraction of nanoparticles. Diffusivity increased as the rotational angle increased, gradually diminishing the influence of nanoparticles. Diffusivity increased drastically as θ changed from 15° to 30° (relative increment in relative diffusivity was almost 3.5 times). Nanoparticles with exfoliation configuration exhibited better oxygen barrier properties compared to intercalation. The finite element model developed in this study provides insight into oxygen barrier properties for nanocomposite with a wide range of structural parameters. This model can be used to design and manufacture an ideal nanocomposite-based food packaging film with improved gas barrier properties for industrial applications. The model will assist in designing nanocomposite polymeric structures of desired gas barrier properties for food packaging applications. In addition, this study will be helpful in formulating a combination of nanoparticle structural parameters for designing nanocomposite membranes with selective permeability for the industrial applications including membrane

Annealing behavior of oxygen in-diffusion from SiO2 film to silicon substrate

International Nuclear Information System (INIS)

Abe, T.; Yamada-Kaneta, H.

2004-01-01

Diffusion behavior of oxygen at (near) the Si/SiO 2 interface was investigated. We first oxidized the floating-zone-grown silicon substrates, and then annealed the SiO 2 -covered substrates in an argon ambient. We examined two different conditions for oxidation: wet and dry oxidation. By the secondary-ion-mass spectrometry, we measured the depth profiles of the oxygen in-diffusion of these heat-treated silicon substrates: We found that the energy of dissolution (in-diffusion) of an oxygen atom that dominates the oxygen concentration at the Si/SiO 2 interface depends on the oxidation condition: 2.0 and 1.7 eV for wet and dry oxidation, respectively. We also found that the barrier heights for the oxygen diffusion in argon anneal were significantly different for different ambients adopted for the SiO 2 formation: 3.3 and 1.8 eV for wet and dry oxidation, respectively. These findings suggest that the microscopic behavior of the oxygen atoms at the Si/SiO 2 interface during the argon anneal depends on the ambient adopted for the SiO 2 formation

The Diffusive Boundary-Layer of Sediments - Oxygen Microgradients Over a Microbial Mat

DEFF Research Database (Denmark)

JØRGENSEN, BB; MARAIS, DJD

1990-01-01

Oxygen microelectrodes were used to analyze the distribution of the diffusive boundary layer (DBL) at the sedimen-water interface in relation to surface topography and flow velocity. The sediment, collected from saline ponds, was covered by a microbial mat that had high oxygen consumption rate...... and well-defined surface structure. Diffusion through the DBL constituted an important rate limitation to the oxygen uptake of the sediment. The mean effective DBL thickness decreased from 0.59 to 0.16 mm as the flow velocity of the overlying water was increased from 0.3 to 7.7 cm s-1 (measured 1 cm above...

Chemical order-disorder in alloys. Study by neutrons diffuse diffusion

International Nuclear Information System (INIS)

Novion, C. de; Beuneu, B.

1993-01-01

Applications of neutrons diffuse diffusion for short distance chemical order in FCC transition metals solid solutions (Pd-V, Ni-V, Ni-Cr) and understoichiometric carbides or nitrides of transition metals (TiC 1-x , NbC 1-x , TiN 1-x ) are shortly presented with theoretical and experimental aspects. (A.B.)

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

Czech Academy of Sciences Publication Activity Database

Jirásek, Vít; Hrubý, Jan; Špalek, Otomar; Čenský, Miroslav; Kodymová, Jarmila

2010-01-01

Roč. 100, č. 4 (2010), s. 779-791 ISSN 0946-2171 Grant - others:European Office of Aerospace R&D(US) FA8655-09-1-3091 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z20760514 Keywords : spray generator of singlet oxygen * singlet oxygen * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.239, year: 2010

Two-photon NADH imaging exposes boundaries of oxygen diffusion in cortical vascular supply regions.

Science.gov (United States)

Kasischke, Karl A; Lambert, Elton M; Panepento, Ben; Sun, Anita; Gelbard, Harris A; Burgess, Robert W; Foster, Thomas H; Nedergaard, Maiken

2011-01-01

Oxygen transport imposes a possible constraint on the brain's ability to sustain variable metabolic demands, but oxygen diffusion in the cerebral cortex has not yet been observed directly. We show that concurrent two-photon fluorescence imaging of endogenous nicotinamide adenine dinucleotide (NADH) and the cortical microcirculation exposes well-defined boundaries of tissue oxygen diffusion in the mouse cortex. The NADH fluorescence increases rapidly over a narrow, very low pO(2) range with a p(50) of 3.4 ± 0.6 mm Hg, thereby establishing a nearly binary reporter of significant, metabolically limiting hypoxia. The transient cortical tissue boundaries of NADH fluorescence exhibit remarkably delineated geometrical patterns, which define the limits of tissue oxygen diffusion from the cortical microcirculation and bear a striking resemblance to the ideal Krogh tissue cylinder. The visualization of microvessels and their regional contribution to oxygen delivery establishes penetrating arterioles as major oxygen sources in addition to the capillary network and confirms the existence of cortical oxygen fields with steep microregional oxygen gradients. Thus, two-photon NADH imaging can be applied to expose vascular supply regions and to localize functionally relevant microregional cortical hypoxia with micrometer spatial resolution.

Two-photon NADH imaging exposes boundaries of oxygen diffusion in cortical vascular supply regions

OpenAIRE

Kasischke, Karl A; Lambert, Elton M; Panepento, Ben; Sun, Anita; Gelbard, Harris A; Burgess, Robert W; Foster, Thomas H; Nedergaard, Maiken

2010-01-01

Oxygen transport imposes a possible constraint on the brain's ability to sustain variable metabolic demands, but oxygen diffusion in the cerebral cortex has not yet been observed directly. We show that concurrent two-photon fluorescence imaging of endogenous nicotinamide adenine dinucleotide (NADH) and the cortical microcirculation exposes well-defined boundaries of tissue oxygen diffusion in the mouse cortex. The NADH fluorescence increases rapidly over a narrow, very low pO2 range with a p ...

Water self-diffusion through narrow oxygenated carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Striolo, Alberto [School of Chemical Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States)

2007-11-28

The hydrophobic interior of carbon nanotubes, which is reminiscent of ion channels in cellular membranes, has inspired scientific research directed towards the production of, for example, membranes for water desalination, drug-delivery devices, and nanosyringes. To develop these technologies it is crucial to understand and predict the equilibrium and transport properties of confined water. We present here a series of molecular dynamics simulation results conducted to understand the extent to which the presence of a few oxygenated active sites, modeled as carbonyls, affects the transport properties of confined water. The model for the carbon nanotube is not intended to be realistic. Its only purpose is to allow us to understand the effect of a few oxygenated sites on the transport properties of water confined in a narrow cylindrical pore, which is otherwise hydrophobic. At low hydration levels we found little, if any, water diffusion. The diffusion, which appears to be of the Fickian type for sufficiently large hydration levels, becomes faster as the number of confined water molecules increases, reaches a maximum, and slows as water fills the carbon nanotubes. We explain our findings on the basis of two collective motion mechanisms observed from the analysis of sequences of simulation snapshots. We term the two mechanisms 'cluster-breakage' and 'cluster-libration' mechanisms. We observe that the cluster-breakage mechanism produces longer displacements for the confined water molecules than the cluster-libration one, but deactivates as water fills the carbon nanotube. From a practical point of view, our results are particularly important for two reasons: (1) at low hydration levels the presence of only eight carbonyl groups can prevent the diffusion of water through (8, 8) carbon nanotubes; and (2) the extremely fast self-diffusion coefficients observed for water within narrow carbon nanotubes are significantly decreased in the presence of only a

Water self-diffusion through narrow oxygenated carbon nanotubes

International Nuclear Information System (INIS)

Striolo, Alberto

2007-01-01

The hydrophobic interior of carbon nanotubes, which is reminiscent of ion channels in cellular membranes, has inspired scientific research directed towards the production of, for example, membranes for water desalination, drug-delivery devices, and nanosyringes. To develop these technologies it is crucial to understand and predict the equilibrium and transport properties of confined water. We present here a series of molecular dynamics simulation results conducted to understand the extent to which the presence of a few oxygenated active sites, modeled as carbonyls, affects the transport properties of confined water. The model for the carbon nanotube is not intended to be realistic. Its only purpose is to allow us to understand the effect of a few oxygenated sites on the transport properties of water confined in a narrow cylindrical pore, which is otherwise hydrophobic. At low hydration levels we found little, if any, water diffusion. The diffusion, which appears to be of the Fickian type for sufficiently large hydration levels, becomes faster as the number of confined water molecules increases, reaches a maximum, and slows as water fills the carbon nanotubes. We explain our findings on the basis of two collective motion mechanisms observed from the analysis of sequences of simulation snapshots. We term the two mechanisms 'cluster-breakage' and 'cluster-libration' mechanisms. We observe that the cluster-breakage mechanism produces longer displacements for the confined water molecules than the cluster-libration one, but deactivates as water fills the carbon nanotube. From a practical point of view, our results are particularly important for two reasons: (1) at low hydration levels the presence of only eight carbonyl groups can prevent the diffusion of water through (8, 8) carbon nanotubes; and (2) the extremely fast self-diffusion coefficients observed for water within narrow carbon nanotubes are significantly decreased in the presence of only a few oxygenated active

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

Energy Technology Data Exchange (ETDEWEB)

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

Molecular dynamics simulation of helium and oxygen diffusion in UO2±x

International Nuclear Information System (INIS)

Govers, K.; Lemehov, S.; Hou, M.; Verwerft, M.

2009-01-01

Atomic scale simulation techniques based on empirical potentials have been considered in the present work to get insight on helium diffusion in uranium dioxide. By varying the stoichiometry, together with the system temperature, the performed molecular dynamics simulations indicate two diffusion regimes for He. The first one presents a low activation energy (0.5 eV) and suggests oxygen vacancies assisted migration. This regime seems to provide the major contribution to diffusion when structural defects are present (extrinsic defects, imposed, e.g. by the stoichiometry). The second regime presents a higher activation energy, around 2 eV, and dominates in the higher temperature range or at perfect stoichiometry, suggesting an intrinsic migration process. Considering the dependence of He behaviour with oxygen defects, oxygen diffusion has been considered as well in the different stoichiometry domains. Finally, further investigations were made with nudged elastic bands calculations for a better interpretation of the operating migration mechanisms, both for He and O.

Characterization of transport properties in uranium dioxide: the case of the oxygen auto-diffusion

International Nuclear Information System (INIS)

Fraczkiewicz, M.; Baldinozzi, G.

2008-01-01

Point defects in uranium dioxide which control the transport phenomena are still badly known. The aim of this work is to show how in carrying out several experimental techniques, it is possible to demonstrate both the existence and to determine the nature (charge and localization) of predominant defects responsible of the transport phenomena in a fluorite-type structure oxide. The oxygen diffusion in the uranium dioxide illustrates this. In the first part of this work, the accent is put on the electric properties of uranium dioxide and more particularly on the variation laws of the electric conductivity in terms of temperature, of oxygen potential and of the impurities amounts present in the material. These evolutions are connected to point and charged complex defects models and the pertinence of these models is discussed. Besides, it is shown how the electric conductivity measurements can allow to define oxygen potential domains in which the concentrations in electronic carriers are controlled. This characterization being made, it is shown that the determination of the oxygen intrinsic diffusion coefficient and particularly its dependence to the oxygen potential and to the amount of impurity, allows to determine the main defect responsible to the atomic diffusion as well as its nature and its charge. In the second part, the experimental techniques to determine the oxygen diffusion coefficient are presented: there are the isotopic exchange technique for introducing the tracer in the material, and two techniques to characterize the diffusion profiles (SIMS and NRA). Examples of preliminary results are given for mono and polycrystalline samples. At last, from this methodology on uranium dioxide, studies considered to quantify the thermal and physicochemical effects are presented. Experiments considered with the aim to characterize the radiation diffusion in uranium dioxide are presented too. (O.M.)

Advanced chemical oxygen iodine lasers for novel beam generation

Science.gov (United States)

Wu, Kenan; Zhao, Tianliang; Huai, Ying; Jin, Yuqi

2018-03-01

Chemical oxygen iodine laser, or COIL, is an impressive type of chemical laser that emits high power beam with good atmospheric transmissivity. Chemical oxygen iodine lasers with continuous-wave plane wave output are well-developed and are widely adopted in directed energy systems in the past several decades. Approaches of generating novel output beam based on chemical oxygen iodine lasers are explored in the current study. Since sophisticated physical processes including supersonic flowing of gaseous active media, chemical reacting of various species, optical power amplification, as well as thermal deformation and vibration of mirrors take place in the operation of COIL, a multi-disciplinary model is developed for tracing the interacting mechanisms and evaluating the performance of the proposed laser architectures. Pulsed output mode with repetition rate as high as hundreds of kHz, pulsed output mode with low repetition rate and high pulse energy, as well as novel beam with vector or vortex feature can be obtained. The results suggest potential approaches for expanding the applicability of chemical oxygen iodine lasers.

Oxygen Permeability and Grain-Boundary Diffusion Applied to Alumina Scales

Science.gov (United States)

Smialek, James L.; Jacobson, Nathan S.; Gleeson, Brian; Hovis, David B.; Heuer, Arthur H.

2013-01-01

High-temperature oxygen permeability measurements had determined grain-boundary diffusivities (deltaD(sub gb)) in bulk polycrystalline alumina (Wada, Matsudaira, and Kitaoka). They predict that oxygen deltaD(sub gb,O) varies with oxygen pressure as P(O2)(sup -1/6) at low pressure whereas aluminum deltaD(sub gb),Al varies with P(O2)(sup +3/16) at high pressure. These relations were used to evaluate alumina scale growth in terms of diffusivity and grain size. A modified Wagner treatment for dominant inward oxygen growth produces the concise solution: ?(sub i) = k(sub p,i)×G(sub i) = 12 deltaD(sub gb,O,int), where ?(sub i) is a constant and k(sub p,i) and G(sub i) refer to instantaneous values of the scale parabolic growth constant and grain size, respectively. A commercial FeCrAl(Zr) alloy was oxidized at 1100 to 1400 degC to determine k(sub p,i), interfacial grain size, ?, and thus deltaD(sub gb,O,int). The deltaD(sub gb,O,int) values predicted from oxidation at (375 kJ/mole) were about 20 times less than those obtained above (at 298 kJ/mole), but closer than extrapolations from high-temperature bulk measurements. The experimental oxidation results agree with similar FeCrAl(X) studies, especially where both k(sub p,i) and G(sub i) were characterized. This complete approach accounts for temperature-sensitive oxidation effects of grain enlargement, equilibrium interface pressure variation, and grain-boundary diffusivity.

Tri-metallic ferrite oxygen carriers for chemical looping combustion

Science.gov (United States)

Siriwardane, Ranjani V.; Fan, Yueying

2017-10-25

The disclosure provides a tri-metallic ferrite oxygen carrier for the chemical looping combustion of carbonaceous fuels. The tri-metallic ferrite oxygen carrier comprises Cu.sub.xFe.sub.yMn.sub.zO.sub.4-.delta., where Cu.sub.xFe.sub.yMn.sub.zO.sub.4-.delta. is a chemical composition. Generally, 0.5.ltoreq.x.ltoreq.2.0, 0.2.ltoreq.y.ltoreq.2.5, and 0.2.ltoreq.z.ltoreq.2.5, and in some embodiments, 0.8.ltoreq.x.ltoreq.1.2, y.ltoreq.1.2, and z.gtoreq.0.8. The tri-metallic ferrite oxygen carrier may be used in various applications for the combustion of carbonaceous fuels, including as an oxygen carrier for chemical looping combustion.

Diffusive flux in a model of stochastically gated oxygen transport in insect respiration

Energy Technology Data Exchange (ETDEWEB)

Berezhkovskii, Alexander M. [Mathematical and Statistical Computing Laboratory, Division of Computational Bioscience, Center for Information Technology, National Institutes of Health, Bethesda, Maryland 20892 (United States); Shvartsman, Stanislav Y. [Department of Chemical and Biological Engineering and Lewis-Sigler Institute for Integrative Genomics, Princeton University, Princeton, New Jersey 08544 (United States)

2016-05-28

Oxygen delivery to insect tissues is controlled by transport through a branched tubular network that is connected to the atmosphere by valve-like gates, known as spiracles. In certain physiological regimes, the spiracles appear to be randomly switching between open and closed states. Quantitative analysis of this regime leads a reaction-diffusion problem with stochastically switching boundary condition. We derive an expression for the diffusive flux at long times in this problem. Our approach starts with the derivation of the passage probability for a single particle that diffuses between a stochastically gated boundary, which models the opening and closing spiracle, and the perfectly absorbing boundary, which models oxygen absorption by the tissue. This passage probability is then used to derive an expression giving the diffusive flux as a function of the geometric parameters of the tube and characteristic time scales of diffusion and gate dynamics.

The Diffusive Boundary-Layer of Sediments - Oxygen Microgradients Over a Microbial Mat

DEFF Research Database (Denmark)

JØRGENSEN, BB; MARAIS, DJD

1990-01-01

Oxygen microelectrodes were used to analyze the distribution of the diffusive boundary layer (DBL) at the sedimen-water interface in relation to surface topography and flow velocity. The sediment, collected from saline ponds, was covered by a microbial mat that had high oxygen consumption rate...

Molecular dynamics simulation of helium and oxygen diffusion in UO{sub 2+}-{sub x}

Energy Technology Data Exchange (ETDEWEB)

Govers, K., E-mail: kgovers@sckcen.b [Service de Metrologie Nucleaire (CP 165/84), Universite Libre de Bruxelles, 50 av. F.D. Roosevelt, B-1050 Bruxelles (Belgium); Institute for Nuclear Materials Sciences, SCK-CEN, Boeretang 200, B-2400 Mol (Belgium); Lemehov, S. [Institute for Nuclear Materials Sciences, SCK-CEN, Boeretang 200, B-2400 Mol (Belgium); Hou, M. [Physique des Solides Irradies et des Nanostructures (CP 234), Universite Libre de Bruxelles, Bd du Triomphe, B-1050 Bruxelles (Belgium); Verwerft, M. [Institute for Nuclear Materials Sciences, SCK-CEN, Boeretang 200, B-2400 Mol (Belgium)

2009-12-15

Atomic scale simulation techniques based on empirical potentials have been considered in the present work to get insight on helium diffusion in uranium dioxide. By varying the stoichiometry, together with the system temperature, the performed molecular dynamics simulations indicate two diffusion regimes for He. The first one presents a low activation energy (0.5 eV) and suggests oxygen vacancies assisted migration. This regime seems to provide the major contribution to diffusion when structural defects are present (extrinsic defects, imposed, e.g. by the stoichiometry). The second regime presents a higher activation energy, around 2 eV, and dominates in the higher temperature range or at perfect stoichiometry, suggesting an intrinsic migration process. Considering the dependence of He behaviour with oxygen defects, oxygen diffusion has been considered as well in the different stoichiometry domains. Finally, further investigations were made with nudged elastic bands calculations for a better interpretation of the operating migration mechanisms, both for He and O.

Investigation of radiation-enhanced oxygen diffusion in Li-Ti ferrites

International Nuclear Information System (INIS)

Surzhikov, A.P.; Pritulov, A.M.; Gyngazov, S.A.; Lysenko, E.N.

1999-01-01

The radiation-enhanced oxygen diffusion in polycrystalline Li-Ti ferrites was investigated. The electron accelerator ELV-6 (Institute of Nuclear Physics, Russian Academy of Sciences) was used to generate the radiothermal annealing. The radiation effects were established by comparison of diffusion profiles of the samples, which were radiothermally treated, and data obtained during the thermal annealing in the resistance furnace. It was discovered that there was an increase of numerical values of Ed (activation diffusion energy) and Do (preexponential factor) during the radiothermal annealing, if compared with the thermal one. The investigations were financed by the Russian Fundamental Research Fund

Diffusion of oxygen in nitrogen in the pores of graphite. Preliminary results on the effect of oxidation on diffusivity

Energy Technology Data Exchange (ETDEWEB)

Hewitt, G. F.; Sharratt, E. W.

1962-10-15

Preliminary results are reported from an experimental study of the effect of burnoff on the diffusivity of oxygen in nitrogen within the pores of graphite. It is found that the ratio of effective diffusivity to ''free gas'' diffusivity changes about four-fold in the range 0-9% total oxidation. The viscous permeability, B₀, increases in almost the same proportion over the same range.

Oxygenation level and hemoglobin concentration in experimental tumor estimated by diffuse optical spectroscopy

Science.gov (United States)

Orlova, A. G.; Kirillin, M. Yu.; Volovetsky, A. B.; Shilyagina, N. Yu.; Sergeeva, E. A.; Golubiatnikov, G. Yu.; Turchin, I. V.

2017-07-01

Using diffuse optical spectroscopy the level of oxygenation and hemoglobin concentration in experimental tumor in comparison with normal muscle tissue of mice have been studied. Subcutaneously growing SKBR-3 was used as a tumor model. Continuous wave fiber probe diffuse optical spectroscopy system was employed. Optical properties extraction approach was based on diffusion approximation. Decreased blood oxygen saturation level and increased total hemoglobin content were demonstrated in the neoplasm. The main reason of such differences between tumor and norm was significant elevation of deoxyhemoglobin concentration in SKBR-3. The method can be useful for diagnosis of tumors as well as for study of blood flow parameters of tumor models with different angiogenic properties.

Coupling effects of chemical stresses and external mechanical stresses on diffusion

International Nuclear Information System (INIS)

Xuan Fuzhen; Shao Shanshan; Wang Zhengdong; Tu Shantung

2009-01-01

Interaction between diffusion and stress fields has been investigated extensively in the past. However, most of the previous investigations were focused on the effect of chemical stress on diffusion due to the unbalanced mass transport. In this work, the coupling effects of external mechanical stress and chemical stress on diffusion are studied. A self-consistent diffusion equation including the chemical stress and external mechanical stress gradient is developed under the framework of the thermodynamic theory and Fick's law. For a thin plate subjected to unidirectional tensile stress fields, the external stress coupled diffusion equation is solved numerically with the help of the finite difference method for one-side and both-side charging processes. Results show that, for such two types of charging processes, the external stress gradient will accelerate the diffusion process and thus increase the value of concentration while reducing the magnitude of chemical stress when the direction of diffusion is identical to that of the stress gradient. In contrast, when the direction of diffusion is opposite to that of the stress gradient, the external stress gradient will obstruct the process of solute penetration by decreasing the value of concentration and increasing the magnitude of chemical stress. For both-side charging process, compared with that without the coupling effect of external stress, an asymmetric distribution of concentration is produced due to the asymmetric mechanical stress field feedback to diffusion.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium.

Science.gov (United States)

Horowitz, Jordan M

2015-07-28

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

First-principles studies on vacancy-modified interstitial diffusion mechanism of oxygen in nickel, associated with large-scale atomic simulation techniques

International Nuclear Information System (INIS)

Fang, H. Z.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Alfonso, D.; Alman, D. E.; Shin, Y. K.; Zou, C. Y.; Duin, A. C. T. van; Lei, Y. K.; Wang, G. F.

2014-01-01

This paper is concerned with the prediction of oxygen diffusivities in fcc nickel from first-principles calculations and large-scale atomic simulations. Considering only the interstitial octahedral to tetrahedral to octahedral minimum energy pathway for oxygen diffusion in fcc lattice, greatly underestimates the migration barrier and overestimates the diffusivities by several orders of magnitude. The results indicate that vacancies in the Ni-lattice significantly impact the migration barrier of oxygen in nickel. Incorporation of the effect of vacancies results in predicted diffusivities consistent with available experimental data. First-principles calculations show that at high temperatures the vacancy concentration is comparable to the oxygen solubility, and there is a strong binding energy and a redistribution of charge density between the oxygen atom and vacancy. Consequently, there is a strong attraction between the oxygen and vacancy in the Ni lattice, which impacts diffusion

Intramyocardial oxygen transport by quantitative diffuse reflectance spectroscopy in calves

Science.gov (United States)

Lindbergh, Tobias; Larsson, Marcus; Szabó, Zoltán; Casimir-Ahn, Henrik; Strömberg, Tomas

2010-03-01

Intramyocardial oxygen transport was assessed during open-chest surgery in calves by diffuse reflectance spectroscopy using a small intramuscular fiber-optic probe. The sum of hemo- and myoglobin tissue fraction and oxygen saturation, the tissue fraction and oxidation of cytochrome aa3, and the tissue fraction of methemoglobin were estimated using a calibrated empirical light transport model. Increasing the oxygen content in the inhaled gas, 21%-50%-100%, in five calves (group A) gave an increasing oxygen saturation of 19+/-4%, 24+/-5%, and 28+/-8% (panimals increased with LVAD pump speed (p<0.001, ANOVA) and with oxygen content in inhaled gas (p<0.001, ANOVA). The cytochrome aa3 oxidation level was above 96% in both group A and group B calves, including the two cases involving cardiac arrest. In conclusion, the estimated tissue fractions and oxygenation/oxidation levels of the myocardial chromophores during respiratory and hemodynamic provocations were in agreement with previously presented results, demonstrating the potential of the method.

Diffusion of oxygen through cork stopper: is it a Knudsen or a Fickian mechanism?

Science.gov (United States)

Lagorce-Tachon, Aurélie; Karbowiak, Thomas; Simon, Jean-Marc; Gougeon, Régis; Bellat, Jean-Pierre

2014-09-17

The aim of this work is to identify which law governs oxygen transfer through cork: Knudsen or Fickian mechanism. This is important to better understand wine oxidation during post-bottling aging. Oxygen transfer through cork wafers is measured at 298 K using a manometric permeation technique. Depending on the mechanism, we can extract the transport coefficients. Increasing the initial pressure of oxygen from 50 to 800 hPa leads to a change in the values of the transport coefficients. This implies that oxygen transport through cork does not obey the Knudsen law. From these results, we conclude that the limiting step of oxygen transport through cork occurs in the cell wall following Fickian law. From the diffusion dependence's coefficients with pressure, we also extract by applying transition state theory an apparent activation volume of 45 ± 4 nm(3). This high value indicates that oxygen molecules also diffuse from one site to another by passing through a gas phase.

Oxygen diffusion-concentration in phospholipidic model membranes. An ESR-saturation study

International Nuclear Information System (INIS)

Vachon, A.; Lecomte, C.; Berleur, F.

1986-04-01

Fully hydrated liposomes of dipalmitoyl-phosphatidylcholine were labelled with 5 (or 7, 10, 12, 16)-doxyl stearic acid at pH 6 and 8, and studied by the continuous wave ESR-saturation technique. The ESR spectral magnitude depends on the hyperfrequency power P and on both T 1 and T 2 relaxation times. Saturation, i.e. the non linearity of the spectral magnitude plotted versus √P can be quantified by a P1/2 parameter (power at which the signal is half as great as it would be without saturation). If we assume T 2 weakly modified by spin exchange between paramagnetic spin probe and oxygen in triplet state, P1/2 is inversely proportional to T 1 , and becomes a sensitive parameter to appreciate the oxygen transport (oxygen diffusion-concentration product) inside the bilayers. According to the DPPC bilayer phase transition diagrams, P1/2 (oxygen diffusion-concentration) is related to the thermodynamic state of the membrane. This technique provides further informations on a particular property of a radioprotective agent, cysteamine, which seems to inhibit spin-triplet exchange and hence maximizes T 1 (minimizes P1/2). Since radioprotective agents are known to act by scavenging radiation-induced free radicals and by inhibiting oxygen-dependent free radical processes, such a result may contribute to elucidate radioprotecting mechanisms

Chemical oxygen demand (cod) attenuation of methyl red in water ...

African Journals Online (AJOL)

Chemical oxygen demand (cod) attenuation of methyl red in water using biocarbons obtained from Nipa palm leaves. ... eco-friendly and locally accessible biocarbon for mitigation of organic contaminants in water. Keywords: Chemical oxygen demand, biocarbon, methyl red, biodegradation, bioremediation, Nipa palm ...

Centrifugal spray generator of singlet oxygen for a chemical oxygen-iodine laser

Czech Academy of Sciences Publication Activity Database

Špalek, Otomar; Hrubý, Jan; Čenský, Miroslav; Jirásek, Vít; Kodymová, Jarmila

2010-01-01

Roč. 100, č. 4 (2010), s. 793-802 ISSN 0946-2171 Grant - others:European Office of Aerospace R&D(US) FA8655-09-1-3091 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z20760514 Keywords : centrifugal generator of singlet oxygen * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.239, year: 2010

Effect of Oxygen Enrichment in Propane Laminar Diffusion Flames under Microgravity and Earth Gravity Conditions

Science.gov (United States)

Bhatia, Pramod; Singh, Ravinder

2017-06-01

Diffusion flames are the most common type of flame which we see in our daily life such as candle flame and match-stick flame. Also, they are the most used flames in practical combustion system such as industrial burner (coal fired, gas fired or oil fired), diesel engines, gas turbines, and solid fuel rockets. In the present study, steady-state global chemistry calculations for 24 different flames were performed using an axisymmetric computational fluid dynamics code (UNICORN). Computation involved simulations of inverse and normal diffusion flames of propane in earth and microgravity condition with varying oxidizer compositions (21, 30, 50, 100 % O2, by mole, in N2). 2 cases were compared with the experimental result for validating the computational model. These flames were stabilized on a 5.5 mm diameter burner with 10 mm of burner length. The effect of oxygen enrichment and variation in gravity (earth gravity and microgravity) on shape and size of diffusion flames, flame temperature, flame velocity have been studied from the computational result obtained. Oxygen enrichment resulted in significant increase in flame temperature for both types of diffusion flames. Also, oxygen enrichment and gravity variation have significant effect on the flame configuration of normal diffusion flames in comparison with inverse diffusion flames. Microgravity normal diffusion flames are spherical in shape and much wider in comparison to earth gravity normal diffusion flames. In inverse diffusion flames, microgravity flames were wider than earth gravity flames. However, microgravity inverse flames were not spherical in shape.

Flow-Injection Responses of Diffusion Processes and Chemical Reactions

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov

2000-01-01

tool of automated analytical chemistry. The need for an even lower consumption of chemicals and for computer analysis has motivated a study of the FIA peak itself, that is, a theoretical model was developed, that provides detailed knowledge of the FIA profile. It was shown that the flow in a FIA...... manifold may be characterised by a diffusion coefficient that depends on flow rate, denoted as the kinematic diffusion coefficient. The description was applied to systems involving species of chromium, both in the case of simple diffusion and in the case of chemical reactions. It is suggested that it may...... be used in the resolution of FIA profiles to obtain information about the content of interference’s, in the study of chemical reaction kinetics and to measure absolute concentrations within the FIA-detector cell....

Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

Science.gov (United States)

Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

2018-01-01

In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

Oxygen diffusion kinetics and reactive lifetimes in bacterial and mammalian cells irradiated with nanosecond pulses of high intensity electrons

International Nuclear Information System (INIS)

Epp, E.R.; Weiss, H.; Ling, C.C.; Djordjevic, B.; Kessaris, N.D.

1975-01-01

Experiaments have been designed to gain information on the lifetime of oxygen-sensitive species suspected to be produced in critical molecules in irradiated cells and on the time-diffusion of oxygen in cells. An approach developed in this laboratory involves the delivery of two high intensity electron pulses each of 3 ns duration to a thin layer of cells equilibrated with a known concentration of oxygen. The first pulse serves to render the cells totally anoxic by the radiochemical depletion of oxygen; the second is delivered at a time electronically delayed after the first allowing for diffusion of oxygen during this time. Under these conditions the radiosensitivity of E coli B/r has been measured over six decades of interpulse time. Cellular time-diffusion curves constructed from the measurements show that oxygen establishes its sensitizing effect within 10 -4 s after the creation of intracellular anoxia establishing this time as an upper limit to the lifetime of the species. Unusual behaviour of the diffusion curve observed for longer delay times can be explained by a model wherein it is postulated that a radiation-induced inhibiting agent slows down diffusion. Application of this model to the experimental data yields a value of 0.4x10 -5 cm 2 s -1 for the cellular oxygen diffusion coefficient. Similar experiments recently carried out for Serratia marcescens will also be described. The oxygen effect in cultured HeLa cells exposed to single short electron pulses has been examined over a range of oxygen concentrations. A family of breaking survival curves was obtained similar to those previously measured for E coli B/r by this laboratory. The data appear to be reasonably consistent with a physicochemical mechanism involving the radiochemical depletion of oxygen previously invoked for bacteria. (author)

The role of oxygen in the deposition of copper–calcium thin film as diffusion barrier for copper metallization

Energy Technology Data Exchange (ETDEWEB)

Yu, Zhinong, E-mail: znyu@bit.edu.cn [School of Optoelectronics and Beijing Engineering Research Center of Mixed Reality and Advanced Display, Beijing Institute of Technology, Beijing 100081 (China); Ren, Ruihuang [School of Optoelectronics and Beijing Engineering Research Center of Mixed Reality and Advanced Display, Beijing Institute of Technology, Beijing 100081 (China); Xue, Jianshe; Yao, Qi; Li, Zhengliang; Hui, Guanbao [Beijing BOE Optoelectronics Technology Co., Ltd, Beijing 100176 (China); Xue, Wei [School of Optoelectronics and Beijing Engineering Research Center of Mixed Reality and Advanced Display, Beijing Institute of Technology, Beijing 100081 (China)

2015-02-15

Highlights: • The CuCa film as the diffusion barrier of Cu film improves the adhesion of Cu film. • The introduction of oxygen into the deposition of CuCa film is necessary to improve the adhesion of Cu film. • The CuCa alloy barrier layer deposited at oxygen atmosphere has perfect anti-diffusion between Cu film and substrate. - Abstract: The properties of copper (Cu) metallization based on copper–calcium (CuCa) diffusion barrier as a function of oxygen flux in the CuCa film deposition were investigated in view of adhesion, diffusion and electronic properties. The CuCa film as the diffusion barrier of Cu film improves the adhesion of Cu film, however, and increases the resistance of Cu film. The introduction of oxygen into the deposition of CuCa film induces the improvement of adhesion and crystallinity of Cu film, but produces a slight increase of resistance. The increased resistance results from the partial oxidation of Cu film. The annealing process in vacuum further improves the adhesion, crystallinity and conductivity of Cu film. X-ray diffraction (XRD) and Auger electron spectroscopy (AES) show that the CuCa alloy barrier layer deposited at oxygen atmosphere has perfect anti-diffusion between Cu film and substrate due to the formation of Ca oxide in the interface of CuCa/substrate.

Introduction of high oxygen concentrations into silicon wafers by high-temperature diffusion

International Nuclear Information System (INIS)

Casse, G.; Glaser, M.; Lemeilleur, F.; Ruzin, A.; Wegrzecki, M.

1999-01-01

The tolerance of silicon detectors to hadron irradiation can be improved by the introduction of a high concentration of oxygen into the starting material. High-resistivity Floating-Zone (FZ) silicon is required for detectors used in particle physics applications. A significantly high oxygen concentration (>10 17 atoms cm -3 ) cannot readily be achieved during the FZ silicon refinement. The diffusion of oxygen at elevated temperatures from a SiO 2 layer grown on both sides of a silicon wafer is a simple and effective technique to achieve high and uniform concentrations of oxygen throughout the bulk of a 300 μm thick silicon wafer

Chemical-Looping Combustion and Gasification of Coals and Oxygen Carrier Development: A Brief Review

Directory of Open Access Journals (Sweden)

Ping Wang

2015-09-01

Full Text Available Chemical-looping technology is one of the promising CO2 capture technologies. It generates a CO2 enriched flue gas, which will greatly benefit CO2 capture, utilization or sequestration. Both chemical-looping combustion (CLC and chemical-looping gasification (CLG have the potential to be used to generate power, chemicals, and liquid fuels. Chemical-looping is an oxygen transporting process using oxygen carriers. Recently, attention has focused on solid fuels such as coal. Coal chemical-looping reactions are more complicated than gaseous fuels due to coal properties (like mineral matter and the complex reaction pathways involving solid fuels. The mineral matter/ash and sulfur in coal may affect the activity of oxygen carriers. Oxygen carriers are the key issue in chemical-looping processes. Thermogravimetric analysis (TGA has been widely used for the development of oxygen carriers (e.g., oxide reactivity. Two proposed processes for the CLC of solid fuels are in-situ Gasification Chemical-Looping Combustion (iG-CLC and Chemical-Looping with Oxygen Uncoupling (CLOU. The objectives of this review are to discuss various chemical-looping processes with coal, summarize TGA applications in oxygen carrier development, and outline the major challenges associated with coal chemical-looping in iG-CLC and CLOU.

Oxygen dynamics and transport in the Mediterranean sponge Aplysina aerophoba

DEFF Research Database (Denmark)

Hoffmann, F.; Røy, Hans; Bayer, K.

2008-01-01

The Mediterranean sponge Aplysina aerophoba kept in aquaria or cultivation tanks can stop pumping for several hours or even days. To investigate changes in the chemical microenvironments, we measured oxygen profiles over the surface and into the tissue of pumping and non-pumping A. aerophoba...... specimens with Clark-type oxygen microelectrodes (tip diameters 18-30 μm). Total oxygen consumption rates of whole sponges were measured in closed chambers. These rates were used to back-calculate the oxygen distribution in a finite-element model. Combining direct measurements with calculations of diffusive...... flux and modeling revealed that the tissue of non-pumping sponges turns anoxic within 15 min, with the exception of a 1 mm surface layer where oxygen intrudes due to molecular diffusion over the sponge surface. Molecular diffusion is the only transport mechanism for oxygen into non-pumping sponges...

Diffusion of oxygen in uranium dioxide: A first-principles investigation

International Nuclear Information System (INIS)

Gupta, Florence; Brillant, Guillaume; Pasturel, Alain

2010-01-01

Results of ab initio density-functional theory calculations of the migration energies of oxygen vacancies and interstitials in stoichiometric UO 2 are reported. The diffusion of oxygen vacancies in UO 2 is found to be highly anisotropic, and the [1 0 0] direction is energetically favored. The atomic relaxations play an important role in reducing the migration barriers. Within the generalized gradient approximation (GGA), we find that the migration energies of the preferred vacancies and interstitials paths are, respectively, 1.18 and 1.09 eV. With the inclusion of the Hubbard U parameter to account for the 5f electron correlations in GGA+U, the vacancy migration energy is lowered to 1.01 eV while the interstitial migration energy increases slightly to 1.13 eV. We find, however, that the correlation effects have a drastic influence on the mechanism of interstitial migration through the stabilization of Willis-type clusters. Indeed, in contrast to GGA, in GGA+U there is an inversion of the migration path with the so-called 'saddle-point' position being lower in energy than the usual starting position. Thus while the migration barriers are nearly the same in GGA and GGA+U, the mechanisms are completely different. Our results clearly indicate that both vacancies and interstitials contribute almost equally to the diffusion of oxygen in UO 2 .

Turbulent diffusion of chemically reacting flows: Theory and numerical simulations.

Science.gov (United States)

Elperin, T; Kleeorin, N; Liberman, M; Lipatnikov, A N; Rogachevskii, I; Yu, R

2017-11-01

The theory of turbulent diffusion of chemically reacting gaseous admixtures developed previously [T. Elperin et al., Phys. Rev. E 90, 053001 (2014)PLEEE81539-375510.1103/PhysRevE.90.053001] is generalized for large yet finite Reynolds numbers and the dependence of turbulent diffusion coefficient on two parameters, the Reynolds number and Damköhler number (which characterizes a ratio of turbulent and reaction time scales), is obtained. Three-dimensional direct numerical simulations (DNSs) of a finite-thickness reaction wave for the first-order chemical reactions propagating in forced, homogeneous, isotropic, and incompressible turbulence are performed to validate the theoretically predicted effect of chemical reactions on turbulent diffusion. It is shown that the obtained DNS results are in good agreement with the developed theory.

Interaction between diffusion and chemical stresses

International Nuclear Information System (INIS)

Yang Fuqian

2005-01-01

The present work studies the interaction between chemical stresses and diffusion. A new relation between hydrostatic stress and concentration of solute atoms is established. For a solid free of action of body force, the Laplacian of the hydrostatic stress is proportional to the Laplacian of the concentration of solute atoms, that is, deviation of the hydrostatic stress from its local average is proportional to deviation of the local concentration of solute atoms. A general relationship among surface concentration of solute atoms, normal stress and surface deformation of a solid is then derived, in which the normal stress is dependent on the mean curvature of the undeformed surface and tangential components of the surface displacement. A closed-form solution of the steady state concentration of solute atoms in a thin plate is obtained. It turns out that linear distribution of solute atoms in the plate is non-existent due to the interaction between chemical stresses and diffusion

Diffusion and solubility of oxygen in γ-ray irradiated polymer insulation materials

International Nuclear Information System (INIS)

Seguchi, Tadao; Yamamoto, Yasuaki.

1986-03-01

The effects of 60 Co γ-rays irradiation on diffusion and solubility of oxygen in polymer materials for electric cable insulation materials were investigated. The polymers were polyethylene, ethylene-propylene rubber, chlorinated polyethylene, chlorosulphonated polyethylene, and chloroprene rubber. They were pure grade and several types of formulation grade. The sheets of these polymers were irradiated up to 5 - 200 Mrad under vacuum or in oxygen under pressure of 3 - 15 atm at room temperature or at 70 deg C. By a method of gas desorption, the diffusion coefficient (D) and solubility coefficient (S) of oxygen or argon in polymer materials were determined at various temperatures of 10 - 80 deg C. The D and S decreased with increase of dose, and the decrease by irradiation with oxidation was more remarkable than that by irradiation without oxidation. However, the decreases of D and S by irradiation were reduced by the formulation of polymers. The additives in formulated polymers would reduce the reactions of crosslinking or oxidation by γ-ray irradiation. The activation energy of D was scarcely changed by irradiations with and without oxidation. (author)

Contributions of chemical and diffusive exchange to T1ρ dispersion.

Science.gov (United States)

Cobb, Jared Guthrie; Xie, Jingping; Gore, John C

2013-05-01

Variations in local magnetic susceptibility may induce magnetic field gradients that affect the signals acquired for MR imaging. Under appropriate diffusion conditions, such fields produce effects similar to slow chemical exchange. These effects may also be found in combination with other chemical exchange processes at multiple time scales. We investigate these effects with simulations and measurements to determine their contributions to rotating frame (R1ρ ) relaxation in model systems. Simulations of diffusive and chemical exchange effects on R1ρ dispersion were performed using the Bloch equations. Additionally, R1ρ dispersion was measured in suspensions of Sephadex and latex beads with varying spin locking fields at 9.4 T. A novel analysis method was used to iteratively fit for apparent chemical and diffusive exchange rates with a model by Chopra et al. Single- and double-inflection points in R1ρ dispersion profiles were observed, respectively, in simulations of slow diffusive exchange alone and when combined with rapid chemical exchange. These simulations were consistent with measurements of R1ρ in latex bead suspensions and small-diameter Sephadex beads that showed single- and double-inflection points, respectively. These observations, along with measurements following changes in temperature and pH, are consistent with the combined effects of slow diffusion and rapid -OH exchange processes. Copyright © 2012 Wiley Periodicals, Inc.

Nitric oxide and carbon monoxide diffusing capacity after a 1-h oxygen dive to 9 m of sea water

NARCIS (Netherlands)

van Ooij, P. J. A. M.; van Hulst, R. A.; Houtkooper, A.; Sterk, P. J.

2014-01-01

To prevent extensive pulmonary lesions in submerged oxygen divers lung function like the forced vital capacity (FVC) or the diffusing capacity for carbon monoxide (DL,co) are used to monitor pulmonary oxygen toxicity (POT). As the diffusing capacity for nitric oxide (DL,no) measures more accurately

Oxygen diffusion coefficient in isolated chicken red and white skeletal muscle fibers in ontogenesis.

Science.gov (United States)

Baranov, V I; Belichenko, V M; Shoshenko, C A

2000-09-01

Oxygen diffusion from medium to cultured isolated muscle fibers from red gastrocnemius muscle (deep part) (RGM) and white pectoralis muscle (WPM) of embryonic and postnatal chickens (about 6 months) was explored. The intracellular effective O(2) diffusion coefficient (D(i)) in muscle fiber was calculated from a model of a cylindrical fiber with a uniform distribution of an oxygen sink based on these experimentally measured parameters: critical tension of O(2) (PO(2)) on the surface of a fiber, specific rate of O(2) consumption by a weight unit of muscle fibers (;VO(2)), and average diameter of muscle fibers. The results document the rapid hypertrophic growth of RGM fibers when compared to WPM fibers in the second half of the embryonic period and the higher values of;VO(2) and critical PO(2) during the ontogenetic period under study. The oxygen D(i) in RGM fibers of embryos and 1-day chickens was two to three times higher than observed for WPM fibers. For senior chickens, the oxygen D(i) value in RGM and WPM fibers does not differ. The D(i) of O(2) in both RGM and WPM fibers increased from 1.4-2.7 x 10(-8) to 90-95 x 10(-8) cm(2)/s with an ontogenetic increase in fiber diameter from 7. 5 to 67.0 microm. At all stages the oxygen D(i) values in RGM and WPM fibers are significantly lower than the O(2) diffusion coefficient in water: for 11-day embryos they are 889 and 1714 times lower and for adult individuals 25 and 27 times lower, respectively. Why oxygen D(i) values in RGM and WPM fibers are so low and why they are gradually increasing during the course of hypertrophic ontogenetic growth are still unclear. Copyright 2000 Academic Press.

Different diffusion mechanisms of oxygen in ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re = Y, Ho) single crystals

Energy Technology Data Exchange (ETDEWEB)

Vovk, R.V.; Boiko, Y.I.; Bogdanov, V.V.; Kamchatnaya, S.N.; Goulatis, I.L. [V. N. Karazin Kharkiv National University, 4 Svobody sq., 61077 Kharkiv (Ukraine); Chroneos, A. [Faculty of Engineering, Environment and Computing, Coventry University, Priory Street, Coventry CV1 5FB (United Kingdom); Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom)

2017-05-15

Highlights: • Single file diffusion mechanism of oxygen ions. • Ho modifies the diffusion mechanism in the oxygen sublattice. • Ho changes the efficient interaction of ions in CuO-planes. - Abstract: In the present study, the time dependencies of the resistivity of ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re=Y, Ho) single crystals with varying degree of deviation from oxygen stoichiometry was investigated. It was shown that the accelerated transport of oxygen ions in the initial stage of the process can be carried out along the one-dimensional non-stoichiometric vacancies’ accumulation by the single file diffusion mechanism. The final phase redistribution of oxygen ions in ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re = Y, Ho) is described by the classical mechanism of volume diffusion. The substitution of yttrium by holmium significantly affects the charge redistribution and changes the efficient interaction of ions in CuO-planes, thereby modifying the mass transfer diffusion mechanisms in the oxygen sublattice. Thus, a significant length change of the time intervals occurs, corresponding to the oxygen ions’ single file and volume diffusion mechanisms.

Thermodynamics and Cation Diffusion in the Oxygen Ion Conductor Lsgm

Science.gov (United States)

Martin, M.; Schulz, O.

Perovskite type oxides based on LaGaO3 are of large technical interest because of their high oxygen-ion conductivity. Lanthanum gallate doped with Sr on A- and Mg on B-sites, La1-xSrxGa1-yMgyO3-(x+y)/2 (LSGM), reaches higher oxygen-ion conductivities than yttria-doped zirconia (YSZ). Thus LSGM represents a promising alternative for YSZ as electrolyte in solid oxide fuel cells (SOFC). Cells using thin LSGM-layers as electrolyte are expected to operate at intermediate temperatures around 700°C for more than 30000 hours without severe degradation. A potential long term degradation effect of LSGM is kinetic demixing of the electrolyte, caused by different cation diffusion coefficients. In this paper we report on experimental studies concerning the phase diagram of LSGM and the diffusion of cations. Cation self-diffusion of 139La, 84Sr and 25Mg and cation impurity diffusion of 144Nd, 89Y and 56Fe in polycrystalline LSGM samples was investigated by secondary ion mass spectrometry (SIMS) for temperatures between 900°C and 1400°C. It was found that diffusion occurs by means of bulk and grain boundaries. The bulk diffusion coefficients are similar for all cations with activation energies which are strongly dependent on temperature. At high temperatures, the activation energies are about 5 eV, while at low temperatures values of about 2 eV are found. These results are explained by a frozen in defect structure at low temperatures. This means that the observed activation energy at low temperatures represents only the migration energy of the different cations while the observed activation energy at high temperatures is the sum of the defect formation energy and the migration energy. The migration energies for all cations are nearly identical, although 139La, 84Sr and 144Nd are occupying A-sites while 25Mg and 56Fe are occupying B-sites in the perovskite-structure. To explain these experimental findings we propose a defect cluster containing cation vacancies in both the A

Enhancement of oxygen diffusion process on a rotating disk electrode for the electro-Fenton degradation of tetracycline

International Nuclear Information System (INIS)

Zhang, Yan; Gao, Ming-Ming; Wang, Xin-Hua; Wang, Shu-Guang; Liu, Rui-Ting

2015-01-01

An electro-Fenton process was developed for wastewater treatment in which hydrogen peroxide was generated in situ with a rotating graphite disk electrode as cathode. The maximum H 2 O 2 generation rate for the RDE reached 0.90 mg/L/h/cm 2 under the rotation speed of 400 rpm at pH 3, and −0.8 V vs SCE. The performance of this electro-Fenton reactor was assessed by tetracycline degradation in an aqueous solution. Experimental results showed the rotation of disk cathode resulted in the efficient production of H 2 O 2 without oxygen aeration, and excellent ability for degrading organic pollutants compared to the electro-Fenton system with fixed cathode. Tetracycline of 50 mg/L was degraded completely within 2 h with the addition of ferrous ion (1.0 mM). The chronoamperometry analysis was employed to investigate the oxygen diffusion on the rotating cathode. The results demonstrated that the diffusion coefficients of dissolved oxygen is 19.45 × 10 −5 cm 2 /s, which is greater than that reported in the literature. Further calculation indicated that oxygen is able to diffuse through the film on the rotating cathode within the contact time in each circle. This study proves that enhancement of oxygen diffusion on RDE is benefit for H 2 O 2 generation, thus provides a promising method for organic pollutants degradation by the combination of RDE with electro-Fenton reactor and offers a new insight on the oxygen transform process in this new system.

Use of Hopcalite derived Cu-Mn mixed oxide as Oxygen Carrier for Chemical Looping with Oxygen Uncoupling Process

OpenAIRE

Adánez-Rubio, Iñaki; Abad Secades, Alberto; Gayán Sanz, Pilar; Adánez-Rubio, Imanol; Diego Poza, Luis F. de; Garcia-Labiano, Francisco; Adánez Elorza, Juan

2016-01-01

Chemical-Looping with Oxygen Uncoupling (CLOU) is an alternative Chemical Looping process for the combustion of solid fuels with inherent CO2 capture. The CLOU process needs a material as oxygen carrier with the ability to give gaseous O2 at suitable temperatures for solid fuel combustion, e.g. copper oxide and manganese oxide. In this work, treated commercial Carulite 300® was evaluated as oxygen carrier for CLOU. Carulite 300® is a hopcalite material composed of 29.2 wt.% CuO and 67.4 wt.% ...

Diazonium Functionalisation of Carbon Nanotubes for Specific Orientation of Multicopper Oxidases: Controlling Electron Entry Points and Oxygen Diffusion to the Enzyme.

Science.gov (United States)

Lalaoui, Noémie; Holzinger, Michael; Le Goff, Alan; Cosnier, Serge

2016-07-18

We report the controlled orientation of bilirubin oxidases (BOD) from Myrothecium verrucaria on multiwalled carbon nanotubes (MWCNTs) functionalised by electrografting of 6-carboxynaphthalenediazonium and 4-(2-aminoethyl)benzenediazonium salts. On negatively charged naphthoate-modified MWCNTs, a high-potential (0.44 V vs. SCE) oxygen reduction electrocatalysis is observed, occurring via the T1 copper centre. On positively charged ammonium-modified MWCNTs, a low-potential (0.15 V) oxygen reduction electrocatalysis is observed, occurring through a partially oxidised state of the T2/T3 trinuclear copper cluster. Finally, chemically modified naphthoate MWCNTs exhibit high bioelectrocatalytic current densities of 3.9 mA cm(-2) under air at gas-diffusion electrode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of trapping parameters and the chemical diffusion coefficient from hydrogen permeation experiments

International Nuclear Information System (INIS)

Svoboda, J.; Mori, G.; Prethaler, A.; Fischer, F.D.

2014-01-01

Highlights: • A modeling study for diffusion of hydrogen with traps is presented. • Introduction of a new chemical diffusion coefficient. • Density of traps and average depth of traps can be determined. • Lattice diffusion and sub-surface concentration of atomic hydrogen can be determined. - Abstract: An improved diffusion theory accounting for trapping effects is applied to evaluation of hydrogen permeation experiments performed for pure iron and pearlitic and martensitic steels. The trapping parameters as molar volume and depth of traps are determined by fitting experiments by simulations based on the theory. The concentration-dependent chemical diffusion coefficient of hydrogen is extracted indicating that the trapping effect on diffusion in pure iron and pearlitic steel is negligible. However, it is significant for martensitic steel, for which the chemical diffusion coefficient cannot be considered as concentration-independent as it is established in current standards

Oxygen vacancies: The origin of n -type conductivity in ZnO

Science.gov (United States)

Liu, Lishu; Mei, Zengxia; Tang, Aihua; Azarov, Alexander; Kuznetsov, Andrej; Xue, Qi-Kun; Du, Xiaolong

2016-06-01

Oxygen vacancy (VO) is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n -type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n -type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

Emergency Evacuation of Hazardous Chemical Accidents Based on Diffusion Simulation

Directory of Open Access Journals (Sweden)

Jiang-Hua Zhang

2017-01-01

Full Text Available The recent rapid development of information technology, such as sensing technology, communications technology, and database, allows us to use simulation experiments for analyzing serious accidents caused by hazardous chemicals. Due to the toxicity and diffusion of hazardous chemicals, these accidents often lead to not only severe consequences and economic losses, but also traffic jams at the same time. Emergency evacuation after hazardous chemical accidents is an effective means to reduce the loss of life and property and to smoothly resume the transport network as soon as possible. This paper considers the dynamic changes of the hazardous chemicals’ concentration after their leakage and simulates the diffusion process. Based on the characteristics of emergency evacuation of hazardous chemical accidents, we build a mixed-integer programming model and design a heuristic algorithm using network optimization and diffusion simulation (hereafter NODS. We then verify the validity and feasibility of the algorithm using Jinan, China, as a computational example. In the end, we compare the results from different scenarios to explore the key factors affecting the effectiveness of the evacuation process.

Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping

Energy Technology Data Exchange (ETDEWEB)

Pan, Wei-Ping; Cao, Yan

2012-11-30

Chemical Looping Combustion (CLC) could totally negate the necessity of pure oxygen by using oxygen carriers for purification of CO{sub 2} stream during combustion. It splits the single fuel combustion reaction into two linked reactions using oxygen carriers. The two linked reactions are the oxidation of oxygen carriers in the air reactor using air, and the reduction of oxygen carriers in the fuel reactor using fuels (i.e. coal). Generally metal/metal oxides are used as oxygen carriers and operated in a cyclic mode. Chemical looping combustion significantly improves the energy conversion efficiency, in terms of the electricity generation, because it improves the reversibility of the fuel combustion process through two linked parallel processes, compared to the conventional combustion process, which is operated far away from its thermo-equilibrium. Under the current carbon-constraint environment, it has been a promising carbon capture technology in terms of fuel combustion for power generation. Its disadvantage is that it is less mature in terms of technological commercialization. In this DOE-funded project, accomplishment is made by developing a series of advanced copper-based oxygen carriers, with properties of the higher oxygen-transfer capability, a favorable thermodynamics to generate high purity of CO{sub 2}, the higher reactivity, the attrition-resistance, the thermal stability in red-ox cycles and the achievement of the auto-thermal heat balance. This will be achieved into three phases in three consecutive years. The selected oxygen carriers with final-determined formula were tested in a scaled-up 10kW coal-fueled chemical looping combustion facility. This scaled-up evaluation tests (2-day, 8-hour per day) indicated that, there was no tendency of agglomeration of copper-based oxygen carriers. Only trace-amount of coke or carbon deposits on the copper-based oxygen carriers in the fuel reactor. There was also no evidence to show the sulphidization of oxygen

Anisotropic chemical strain in cubic ceria due to oxygen-vacancy-induced elastic dipoles.

Science.gov (United States)

Das, Tridip; Nicholas, Jason D; Sheldon, Brian W; Qi, Yue

2018-06-06

Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO2-δ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO2-δ. The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce3+-O bonds elongate, one of the Ce3+-O bond shorten, and all seven of the Ce4+-O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO2-δ. Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry.

Oxygen diffusion process in a Ba{sub 0.96}La{sub 0.04}SnO{sub 3} thin film on SrTiO{sub 3}(001) substrate as investigated by time-dependent Hall effect measurements

Energy Technology Data Exchange (ETDEWEB)

Lee, Woong-Jhae; Kim, Hyung Joon; Sohn, Egon; Kim, Tai Hoon [Department of Physics and Astronomy, Center for Novel States of Complex Materials Research, Seoul National University, Seoul, 151-747 (Korea, Republic of); Kim, Hoon Min; Char, Kookrin [Institute of Applied Physics, Seoul National University, Seoul, 151-747 (Korea, Republic of); Kim, Jin Hyeok [Department of Materials Science and Engineering, Chonnam National University, Gwangju, 500-757 (Korea, Republic of); Kim, Kee Hoon [Department of Physics and Astronomy, Center for Novel States of Complex Materials Research, Seoul National University, Seoul, 151-747 (Korea, Republic of); Institute of Applied Physics, Seoul National University, Seoul, 151-747 (Korea, Republic of)

2015-07-15

We investigate the oxygen diffusion phenomena in a Ba{sub 0.96}La{sub 0.04}SnO{sub 3} (BLSO) thin film on SrTiO{sub 3}(001) substrate by measurements of time-dependent Hall effect at high temperatures around 500 C under different gas atmosphere. Under the Ar (O{sub 2}) atmosphere, carrier density (n) and electrical conductivity (σ) are increased (decreased) while electron mobility (μ) is slightly reduced (enhanced). This observation supports that although both n and μ are affected by the oxygen diffusion process, the change of n is a major factor of determining σ in the BLSO film. Detailed analyses of the time-dependent n exhibit fast and slow dynamics that possibly correspond to the oxygen exchange reaction at the surface and oxygen diffusion into the BLSO grains, respectively. Fitting the time dependence of n reveals that the chemical diffusion coefficient of oxygen in the BLSO grains becomes ∝10{sup -16} cm{sup 2} s{sup -1}. This coefficient marks the lowest value among perovskite oxides around 500 C, directly proving excellent thermal stability of oxygen in BLSO. The present results support that the donor-doped BaSnO{sub 3} system could be useful for realizing transparent semiconductor devices at high temperatures. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Measurement of chemical diffusion coefficients in liquid binary alloys

International Nuclear Information System (INIS)

Keita, M.; Steinemann, S.; Kuenzi, H.U.

1976-01-01

New measurements of the chemical diffusion coefficient in liquid binary alloys are presented. The wellknown geometry of the 'capillary-reservoir' is used and the concentration is obtained from a resistivity measurement. The method allows to follow continuously the diffusion process in the liquid state. A precision of at least 10% in the diffusion coefficient is obtained with a reproductibility better than 5%. The systems Hg-In, Al-Sn, Al-Si have been studied. Diffusion coefficients are obtained as a function of temperature, concentration, and geometrical factors related to the capillary (diameter, relative orientation of density gradient and gravity). (orig.) [de

Diffusion Limitation and Hyperoxic Enhancement of Oxygen Consumption in Zooxanthellate Sea Anemones, Zoanthids, and Corals.

Science.gov (United States)

Shick, J M

1990-08-01

Depending on their size and morphology, anthozoan polyps and colonies may be diffusion-limited in their oxygen consumption, even under well-stirred, air-saturated conditions. This is indicated by an enhancement of oxygen consumption under steady-state hyperoxic conditions that simulate the levels of O2 produced photosynthetically by zooxanthellae in the hosts' tissues. Such hyperoxia in the tissues of zooxanthellate species negates the effect of the diffusive boundary layer, and increases the rate of oxygen consumption; thus, in many cases, the rate of respiration measured under normoxia in the dark may not be representative of the rate during the day when the zooxanthellae are photosynthesizing and when the supply of oxygen for respiration is in the tissues themselves, not from the environment. These results have implications in respirometric methodology and in calculating the rate of gross photosynthesis in energetic studies. The activity of cytochrome c oxidase is higher in aposymbiotic than in zooxanthellate specimens of the sea anemone Aiptasia pulchella, and this may indicate a compensation for the relative hypoxia in the tissues of the former, enhancing the delivery of oxygen to the mitochondria from the environment.

Determination of the diffusion coefficient of oxygen in sodium chloride solutions with a transient pulse technique

NARCIS (Netherlands)

van Stroe, A.J.; Janssen, L.J.J.

1993-01-01

An accurate and rapid method for detg. the diffusion coeffs. of electrochem. active gases in electrolytes is described. The technique is based on chronoamperometry where transient currents are measured and interpreted with a Cottrell-related equation. The diffusion coeffs. of oxygen were detd. for

Diffusion of a multi-species component and its role in oxygen and water transport in silicates

Science.gov (United States)

Zhang, Youxue; Stolper, E. M.; Wasserburg, G. J.

1991-01-01

The diffusion of a multispecies component is complicated by the different diffusion coefficient of each species and the interconversion reactions among the species. A diffusion equation is derived that incorporates the diffusive fluxes of all species contributing to the component's concentration. The effect of speciation on diffusion is investigated experimentally by measuring concentration profiles of all species developed during diffusion experiments. Data on water diffusion in rhyolitic glasses indicate that H2O molecules predominate over OH groups as the diffusing species at very low to high water concentrations. A simple theoretical relationship is drawn between the effective total oxygen diffusion coefficient and the total water concentration of silicates at low water content.

Chemical diffusion on solid surfaces. Final report

International Nuclear Information System (INIS)

Hudson, J.B.

1980-12-01

The techniques of surface science have been applied to the problem of the measurement of the surface diffusion rate of an adsorbed species over the surface of a chemically dissimilar material. Studies were carried out for hydrogen and nitrogen adatoms on a Ni(100) surface and for silver adatoms on a sapphire surface. Positive results were obtained only for the case of nitrogen on Ni(100). In this system the diffusivity is characterized by the expression D = D 0 exp (/sup -ΔH//RT), with D 0 = 0.25 cm 2 /sec and ΔH = 28kcal/mol

A pile-up phenomenon during arsenic diffusion in silicon-on-insulator structures formed by oxygen implantation

Science.gov (United States)

Normand, P.; Tsoukalas, D.; Guillemot, N.; Chenevier, P.

1989-10-01

Arsenic diffusion in silicon-on-insulator formed by deep oxygen implantation is studied by secondary ion mass spectroscopy and speading resistance measurements. An enhanced diffusivity as well as a pile-up phenomenon are observed in the thin silicon layer. The McNabb and Foster equations [Trans. TMS-AIME 22, 618 (1963)] for diffusion with trapping are solved in order to simulate this last effect.

Oxygen-induced high diffusion rate of magnesium dopants in GaN/AlGaN based UV LED heterostructures.

Science.gov (United States)

Michałowski, Paweł Piotr; Złotnik, Sebastian; Sitek, Jakub; Rosiński, Krzysztof; Rudziński, Mariusz

2018-05-23

Further development of GaN/AlGaN based optoelectronic devices requires optimization of the p-type material growth process. In particular, uncontrolled diffusion of Mg dopants may decrease the performance of a device. Thus it is meaningful to study the behavior of Mg and the origins of its diffusion in detail. In this work we have employed secondary ion mass spectrometry to study the diffusion of magnesium in GaN/AlGaN structures. We show that magnesium has a strong tendency to form Mg-H complexes which immobilize Mg atoms and restrain their diffusion. However, these complexes are not present in samples post-growth annealed in an oxygen atmosphere or Al-rich AlGaN structures which naturally have a high oxygen concentration. In these samples, more Mg atoms are free to diffuse and thus the average diffusion length is considerably larger than for a sample annealed in an inert atmosphere.

Atom interaction propensities of oxygenated chemical functions in crystal packings

Directory of Open Access Journals (Sweden)

Christian Jelsch

2017-03-01

Full Text Available The crystal contacts of several families of hydrocarbon compounds substituted with one or several types of oxygenated chemical groups were analyzed statistically using the Hirshfeld surface methodology. The propensity of contacts to occur between two chemical types is described with the contact enrichment descriptor. The systematic large enrichment ratios of some interactions like the O—H...O hydrogen bonds suggests that these contacts are a driving force in the crystal packing formation. The same statement holds for the weaker C—H...O hydrogen bonds in ethers, esters and ketones, in the absence of polar H atoms. The over-represented contacts in crystals of oxygenated hydrocarbons are generally of two types: electrostatic attractions (hydrogen bonds and hydrophobic interactions. While Cl...O interactions are generally avoided, in a minority of chloro-oxygenated hydrocarbons, significant halogen bonding does occur. General tendencies can often be derived for many contact types, but outlier compounds are instructive as they display peculiar or rare features. The methodology also allows the detection of outliers which can be structures with errors. For instance, a significant number of hydroxylated molecules displaying over-represented non-favorable oxygen–oxygen contacts turned out to have wrongly oriented hydroxyl groups. Beyond crystal packings with a single molecule in the asymmetric unit, the behavior of water in monohydrate compounds and of crystals with Z′ = 2 (dimers are also investigated. It was found in several cases that, in the presence of several oxygenated chemical groups, cross-interactions between different chemical groups (e.g. water/alcohols; alcohols/phenols are often favored in the crystal packings. While some trends in accordance with common chemical principles are retrieved, some unexpected results can however appear. For example, in crystals of alcohol–phenol compounds, the strong O—H...O hydrogen bonds between

Accelerated ceria–zirconia solubilization by cationic diffusion inversion at low oxygen activity

DEFF Research Database (Denmark)

Esposito, Vincenzo; Ni, De Wei; Marani, Debora

2016-01-01

Fast elemental diffusion at the Gd-doped ceria/Y-stabilized zirconia interface occurs under reducing conditions at low oxygen activity (pO2 < 10−12 atm) and high temperature (1400 °C). This effect leads to formation of thick ceria–zirconia solid solution reaction layers in the micro-range vs. thi...

Development of high power chemical oxygen lodine laser

Energy Technology Data Exchange (ETDEWEB)

Kim, Cheol Jung; Choi, Y. D.; Chung, C. M.; Kim, M. S.; Baik, S. H.; Kwon, S. O.; Park, S. K.; Kim, T. S

2001-10-01

This project is directed to construct 10kW Chemical Oxygen Iodine Laser (COIL) for decommissioning of old nuclear facilities, and to get the key technology that can be used for the development of high energy laser weapon. COIL is possible up to MW class in proportion to the amount of chemical reaction. For this reason, high energy laser weapon including Airborne Laser (ABL) and Airborne Tactical Laser (ATL) has been developed as a military use in USA. Recently, many research group have been doing a development study of COIL for nuclear and industrial use in material processing such as cutting and decommissioning by combining laser beam delivery through optical fiber. The Chemical Oxygen Iodine Laser of 6 kW output power has been developed in this project. The main technologies of chemical reaction and supersonic fluid control were developed. This technology can be applied for construction of 10 kW laser system. This laser can be used for old nuclear facilities and heavy industry by combining laser beam delivery through optical fiber. The development of High Energy Laser (HEL) weapon is necessary as a military use, and we conclude that Airborne Tactical Laser should be developed in our country.

Limited Influence of Oxygen on the Evolution of Chemical Diversity in Metabolic Networks

Directory of Open Access Journals (Sweden)

Kazuhiro Takemoto

2013-10-01

Full Text Available Oxygen is thought to promote species and biomolecule diversity. Previous studies have suggested that oxygen expands metabolic networks by acquiring metabolites with different chemical properties (higher hydrophobicity, for example. However, such conclusions are typically based on biased evaluation, and are therefore non-conclusive. Thus, we re-investigated the effect of oxygen on metabolic evolution using a phylogenetic comparative method and metadata analysis to reduce the bias as much as possible. Notably, we found no difference in metabolic network expansion between aerobes and anaerobes when evaluating phylogenetic relationships. Furthermore, we showed that previous studies have overestimated or underestimated the degrees of differences in the chemical properties (e.g., hydrophobicity between oxic and anoxic metabolites in metabolic networks of unicellular organisms; however, such overestimation was not observed when considering the metabolic networks of multicellular organisms. These findings indicate that the contribution of oxygen to increased chemical diversity in metabolic networks is lower than previously thought; rather, phylogenetic signals and cell-cell communication result in increased chemical diversity. However, this conclusion does not contradict the effect of oxygen on metabolic evolution; instead, it provides a deeper understanding of how oxygen contributes to metabolic evolution despite several limitations in data analysis methods.

Effect of annealing on structural changes and oxygen diffusion in amorphous HfO2 using classical molecular dynamics

Science.gov (United States)

Shen, Wenqing; Kumari, Niru; Gibson, Gary; Jeon, Yoocharn; Henze, Dick; Silverthorn, Sarah; Bash, Cullen; Kumar, Satish

2018-02-01

Non-volatile memory is a promising alternative to present memory technologies. Oxygen vacancy diffusion has been widely accepted as one of the reasons for the resistive switching mechanism of transition-metal-oxide based resistive random access memory. In this study, molecular dynamics simulation is applied to investigate the diffusion coefficient and activation energy of oxygen in amorphous hafnia. Two sets of empirical potential, Charge-Optimized Many-Body (COMB) and Morse-BKS (MBKS), were considered to investigate the structural and diffusion properties at different temperatures. COMB predicts the activation energy of 0.53 eV for the temperature range of 1000-2000 K, while MBKS predicts 2.2 eV at high temperature (1600-2000 K) and 0.36 eV at low temperature (1000-1600 K). Structural changes and appearance of nano-crystalline phases with increasing temperature might affect the activation energy of oxygen diffusion predicted by MBKS, which is evident from the change in coordination number distribution and radial distribution function. None of the potentials make predictions that are fully consistent with density functional theory simulations of both the structure and diffusion properties of HfO2. This suggests the necessity of developing a better multi-body potential that considers charge exchange.

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

Science.gov (United States)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect.

Science.gov (United States)

Yao, Xiahui; Dong, Qi; Cheng, Qingmei; Wang, Dunwei

2016-09-12

As an electrochemical energy-storage technology with the highest theoretical capacity, lithium-oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round-trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium-oxygen batteries for high-performance operations and how to eventually materialize the full potentials of this promising technology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Critical role for mesoscale eddy diffusion in supplying oxygen to hypoxic ocean waters

Science.gov (United States)

Gnanadesikan, Anand; Bianchi, Daniele; Pradal, Marie-Aude

2013-10-01

of the oceanic lateral eddy diffusion coefficient Aredi vary by more than an order of magnitude, ranging from less than a few hundred m2/s to thousands of m2/s. This uncertainty has first-order implications for the intensity of oceanic hypoxia, which is poorly simulated by the current generation of Earth System Models. Using satellite-based estimate of oxygen consumption in hypoxic waters to estimate the required diffusion coefficient for these waters gives a value of order 1000 m2/s. Varying Aredi across a suite of Earth System Models yields a broadly consistent result given a thermocline diapycnal diffusion coefficient of 1 × 10-5 m2/s.

Photosensitized Oxygenations of Hexamethylbenzene in Phase Contact Enhanced Microreactor

International Nuclear Information System (INIS)

Park, Chan Yi; Park, Jeong Hyeon; Lim Hyo Jin; Hwang, Geumsook; Park, Chan Pil

2014-01-01

Activated singlet oxygen ( 1 O 2 ) has successfully been utilized in production of various compounds including fragrances, pharmaceuticals, and fine chemicals. However, the traditional reaction required a prolonged reaction time due to the difficulty of introducing adequate light and oxygen into the solution. Low contact probability between four species of oxygen, photosensitizer, light, and reagent is an inherent drawback of the traditional photoreaction. Molecular diffusion distance is the most important factor in the heterogeneous reactions including gas-liquid, gassolid, liquid-solid, and immiscible liquid-liquid. Therefore, rates of reaction are closely depended on the distance. Microreactor has provided a distinct advantage in the short molecular diffusion distance due to the high surface-to-volume ratio driven by narrow fluidic channels

Determination of oxygen nonstoichiometry and diffusivity in mixed conducting oxides by oxygen Coulometric titration. II. Oxygen nonstoichiometry and defect model for La0.8Sr0.2CoO3-d

NARCIS (Netherlands)

Lankhorst, M.H.R.; Lankhorst, M.H.R.; Bouwmeester, Henricus J.M.

1997-01-01

The oxygen nonstoichiometry of La0.8Sr0.2CoO3-delta has been determined as a function of oxygen partial pressure and temperature using a high-temperature coulometric titration cell. For each measured value of the oxygen chemical potential, the oxygen nonstoichiometry is found to be nearly

Chemical shifts of oxygen-17 NMR in polyoxotungstates

International Nuclear Information System (INIS)

Kazanskij, L.P.; Fedotov, M.A.; Spitsyn, V.I.

1977-01-01

17 O NMR spectra of aqueous solutions containing paratungstate BH 2 W 12 O 42 10- and metatungstate H 2 W 12 O 40 6- anions have been measured. On the basis of the obtained data a scale of chemical shifts for oxygen atoms connected by various bonds with tungsten atoms is suggested. The obtained data are compared with the Raman spectra of crystalline salts and their aqueous solutions. Chemical shifts of 17 O NMR spectra have been also measured in other heteropolyanions

A coupled theory for chemically active and deformable solids with mass diffusion and heat conduction

Science.gov (United States)

Zhang, Xiaolong; Zhong, Zheng

2017-10-01

To analyse the frequently encountered thermo-chemo-mechanical problems in chemically active material applications, we develop a thermodynamically-consistent continuum theory of coupled deformation, mass diffusion, heat conduction and chemical reaction. Basic balance equations of force, mass and energy are presented at first, and then fully coupled constitutive laws interpreting multi-field interactions and evolving equations governing irreversible fluxes are constructed according to the energy dissipation inequality and the chemical kinetics. To consider the essential distinction between mass diffusion and chemical reactions in affecting free energy and dissipations of a highly coupled system, we regard both the concentrations of diffusive species and the extent of reaction as independent state variables. This new formulation then distinguishes between the energy contribution from the diffusive species entering the solid and that from the subsequent chemical reactions occurring among these species and the host solid, which not only interact with stresses or strains in different manners and on different time scales, but also induce different variations of solid microstructures and material properties. Taking advantage of this new description, we further establish a specialized isothermal model to predict precisely the transient chemo-mechanical response of a swelling solid with a proposed volumetric constraint that accounts for material incompressibility. Coupled kinetics is incorporated to capture the volumetric swelling of the solid caused by imbibition of external species and the simultaneous dilation arised from chemical reactions between the diffusing species and the solid. The model is then exemplified with two numerical examples of transient swelling accompanied by chemical reaction. Various ratios of characteristic times of diffusion and chemical reaction are taken into account to shed light on the dependency on kinetic time scales of evolution patterns for

Reaction diffusion and solid state chemical kinetics handbook

CERN Document Server

Dybkov, V I

2010-01-01

This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

Science.gov (United States)

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

A compartment model of alveolar-capillary oxygen diffusion with ventilation-perfusion gradient and dynamics of air transport through the respiratory tract.

Science.gov (United States)

Jaworski, Jacek; Redlarski, Grzegorz

2014-08-01

This paper presents a model of alveolar-capillary oxygen diffusion with dynamics of air transport through the respiratory tract. For this purpose electrical model representing the respiratory tract mechanics and differential equations representing oxygen membrane diffusion are combined. Relevant thermodynamic relations describing the mass of oxygen transported into the human body are proposed as the connection between these models, as well as the influence of ventilation-perfusion mismatch on the oxygen diffusion. The model is verified based on simulation results of varying exercise intensities and statistical calculations of the results obtained during various clinical trials. The benefit of the approach proposed is its application in simulation-based research aimed to generate quantitative data of normal and pathological conditions. Based on the model presented, taking into account many essential physiological processes and air transport dynamics, comprehensive and combined studies of the respiratory efficiency can be performed. The impact of physical exercise, precise changes in respiratory tract mechanics and alterations in breathing pattern can be analyzed together with the impact of various changes in alveolar-capillary oxygen diffusion. This may be useful in simulation of effects of many severe medical conditions and increased activity level. Copyright © 2014 Elsevier Ltd. All rights reserved.

Emergency Evacuation of Hazardous Chemical Accidents Based on Diffusion Simulation

OpenAIRE

Jiang-Hua Zhang; Hai-Yue Liu; Rui Zhu; Yang Liu

2017-01-01

The recent rapid development of information technology, such as sensing technology, communications technology, and database, allows us to use simulation experiments for analyzing serious accidents caused by hazardous chemicals. Due to the toxicity and diffusion of hazardous chemicals, these accidents often lead to not only severe consequences and economic losses, but also traffic jams at the same time. Emergency evacuation after hazardous chemical accidents is an effective means to reduce the...

Diffusion of Oxygen in Alginate Gels Related to the Kinetics of Methanol Oxidation by Immobilized Hansenula polymorpha Cells

NARCIS (Netherlands)

Hiemstra, Harry; Dijkhuizen, Lubbert; Harder, Willem

1983-01-01

In the yeast Hansenula polymorpha an oxygen-requiring enzyme, alcohol oxidase, catalyzes the conversion of methanol into formaldehyde. After growth on methanol cells of the organism were harvested and entrapped in barium-alginate gels. The diffusion of oxygen towards these cells is seriously

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

Science.gov (United States)

Szumila, Ian; Danielson, Lisa; Trail, Dustin

2017-01-01

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Moving boundary - Oxygen diffusion. Two algorithms using Landau transformation

International Nuclear Information System (INIS)

Moyano, E.A.

1991-01-01

A description is made of two algorithms which solve a mathematical model destinated for the study of one-dimensional problems with moving boundaries and implicit boundary conditions. The Landau transformation is used in both methods for each temporal level so as to work all through with the same amount of nodes. Thus, it is necessary to deal with a partial differential equation whose diffusive and convective terms are accompanied by variable coefficients. The partial differential equation is made discrete implicitly, using the Laasonen scheme -which is always stable- instead of the Crank-Nicholson scheme, as performed by Ferris and Hill (5), in the fixed time passing method. The second method employs the tridiagonal algorithm. The first algorithm uses fixed time passing and iterates with variable interface positions, that is to say, it varies δs until it satisfies the boundary condition. The mathematical model describes oxygen diffusion in live tissues. Its numerical solution is obtained by finite differences. An important application of this method could be the estimation of the radiation dose in cancerous tumor treatment. (Author) [es

Determination of diffusion coefficients of oxygen atoms in ZrO2 using first-principles calculations

International Nuclear Information System (INIS)

Segi, Takashi; Okuda, Takanari

2014-01-01

Density functional theory and nudged elastic band calculations were performed in order to determine the diffusion coefficient for oxygen from monoclinic ZrO 2 . The calculated values for monoclinic ZrO 2 at 1000 K and 1500 K were 5.88 × 10 -16 cm 2 s -1 and 2.91 × 10 -11 cm 2 s -1 , respectively, and agreed with previously determined experimental values. In addition, the results of the nudged elastic band calculations suggest that interstitial oxygen sites exist between stable oxygen sites, and if oxygen atoms occupy these sites, stable structures with values for the lattice angle β of greater than 80.53° may be obtained. (author)

Heat Diffusion in Gases, Including Effects of Chemical Reaction

Science.gov (United States)

Hansen, C. Frederick

1960-01-01

The diffusion of heat through gases is treated where the coefficients of thermal conductivity and diffusivity are functions of temperature. The diffusivity is taken proportional to the integral of thermal conductivity, where the gas is ideal, and is considered constant over the temperature interval in which a chemical reaction occurs. The heat diffusion equation is then solved numerically for a semi-infinite gas medium with constant initial and boundary conditions. These solutions are in a dimensionless form applicable to gases in general, and they are used, along with measured shock velocity and heat flux through a shock reflecting surface, to evaluate the integral of thermal conductivity for air up to 5000 degrees Kelvin. This integral has the properties of a heat flux potential and replaces temperature as the dependent variable for problems of heat diffusion in media with variable coefficients. Examples are given in which the heat flux at the stagnation region of blunt hypersonic bodies is expressed in terms of this potential.

A coupled model between mechanical deformation and chemical diffusion: An explanation for the preservation of chemical zonation in plagioclase at high temperatures

Science.gov (United States)

Zhong, Xin; Vrijmoed, Johannes; Moulas, Evangelos; Tajcmanová, Lucie

2016-04-01

Compositional zoning in metamorphic minerals have been generally recognized as an important geological feature to decipher the metamorphic history of rocks. The observed chemical zoning of, e.g. garnet, is commonly interpreted as disequilibrium between the fractionated inner core and the surrounding matrix. However, chemically zoned minerals were also observed in high grade rocks (T>800 degree C) where the duration of metamorphic processes was independently dated to take several Ma. This implies that temperature may not be the only factor that controls diffusion timescales, and grain scale pressure variation was proposed to be a complementary factor that may significantly contribute to the formation and preservation of chemical zoning in high temperature metamorphic minerals [Tajcmanová 2013, 2015]. Here, a coupled model is developed to simulate viscous deformation and chemical diffusion. The numerical approach considers the conservation of mass, momentum, and a constitutive relation developed from equilibrium thermodynamics. A compressible viscoelastic rheology is applied, which associates the volumetric change triggered by deformation and diffusion to a change of pressure. The numerical model is applied to the chemically zoned plagioclase rim described by [Tajcmanová 2014]. The diffusion process operating during the plagioclase rim formation can lead to a development of a pressure gradient. Such a pressure gradient, if maintained during ongoing viscous relaxation, can lead to the preservation of the observed chemical zonation in minerals. An important dimensionless number, the Deborah number, is defined as the ratio between the Maxwell viscoelastic relaxation time and the characteristic diffusion time. It characterizes the relative influence between the maintenance of grain scale pressure variation and chemical diffusion. Two extreme regimes are shown: the mechanically-controlled regime (high Deborah number) and diffusion-controlled regime (low Deborah number

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Science.gov (United States)

Pfrang, C.; Shiraiwa, M.; Pöschl, U.

2011-07-01

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Directory of Open Access Journals (Sweden)

C. Pfrang

2011-07-01

Full Text Available Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Untangling surface oxygen exchange effects in YBa2Cu3O6+x thin films by electrical conductivity relaxation.

Science.gov (United States)

Cayado, P; Sánchez-Valdés, C F; Stangl, A; Coll, M; Roura, P; Palau, A; Puig, T; Obradors, X

2017-05-31

The kinetics of oxygen incorporation (in-diffusion process) and excorporation (out-diffusion process), in YBa 2 Cu 3 O 6+x (YBCO) epitaxial thin films prepared using the chemical solution deposition (CSD) methodology by the trifluoroacetate route, was investigated by electrical conductivity relaxation measurements. We show that the oxygenation kinetics of YBCO films is limited by the surface exchange process of oxygen molecules prior to bulk diffusion into the films. The analysis of the temperature and oxygen partial pressure influence on the oxygenation kinetics has drawn a consistent picture of the oxygen surface exchange process enabling us to define the most likely rate determining step. We have also established a strategy to accelerate the oxygenation kinetics at low temperatures based on the catalytic influence of Ag coatings thus allowing us to decrease the oxygenation temperature in the YBCO thin films.

Anion and cation diffusion in barium titanate and strontium titanate

International Nuclear Information System (INIS)

Kessel, Markus Franz

2012-01-01

Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO 3 single crystals has been studied by means of 18 O 2 / 16 O 2 isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material's bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial pressure and temperature. The

On some limitations of reaction-diffusion chemical computers in relation to Voronoi diagram and its inversion

International Nuclear Information System (INIS)

Adamatzky, Andrew; Lacy Costello, Benjamin de

2003-01-01

A reaction-diffusion chemical computer in this context is a planar uniform chemical reactor, where data and results of a computation are represented by concentration profiles of reactants and the computation itself is implemented via the spreading and interaction of diffusive and phase waves. This class of chemical computers are efficient at solving problems with a 'natural' parallelism where data sets are decomposable onto a large number of geographically neighboring domains which are then processed in parallel. Typical problems of this type include image processing, geometrical transformations and optimisation. When chemical based devices are used to solve such problems questions regarding their reproducible, efficiency and the accuracy of their computations arise. In addition to these questions what are the limitations of reaction-diffusion chemical processors--what type of problems cannot currently and are unlikely ever to be solved? To answer the questions we study how a Voronoi diagram is constructed and how it is inverted in a planar chemical processor. We demonstrate that a Voronoi diagram is computed only partially in the chemical processor. We also prove that given a specific Voronoi diagram it is impossible to reconstruct the planar set (from which diagram was computed) in the reaction-diffusion chemical processor. In the Letter we open the first ever line of enquiry into the computational inability of reaction-diffusion chemical computers

Thermally activated reaction–diffusion-controlled chemical bulk reactions of gases and solids

Directory of Open Access Journals (Sweden)

S. Möller

2015-01-01

Full Text Available The chemical kinetics of the reaction of thin films with reactive gases is investigated. The removal of thin films using thermally activated solid–gas to gas reactions is a method to in-situ control deposition inventory in vacuum and plasma vessels. Significant scatter of experimental deposit removal rates at apparently similar conditions was observed in the past, highlighting the need for understanding the underlying processes. A model based on the presence of reactive gas in the films bulk and chemical kinetics is presented. The model describes the diffusion of reactive gas into the film and its chemical interaction with film constituents in the bulk using a stationary reaction–diffusion equation. This yields the reactive gas concentration and reaction rates. Diffusion and reaction rate limitations are depicted in parameter studies. Comparison with literature data on tokamak co-deposit removal results in good agreement of removal rates as a function of pressure, film thickness and temperature.

Twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+x studied by neutron powder diffraction and gas volumetry

Science.gov (United States)

Poulsen, H. F.; Andersen, N. H.; Lebech, B.

1991-02-01

We report experimental results of twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+ x, which supplement a previous and simultaneous study of the structural phase diagram and oxygen equilibrium partial pressure. Analysis of neutron powder diffraction peak broadening show features which are identified to result from temperature independent twin-domain formation in to different orthorhombic phases with domain sizes and 250 and 350Å, respectively. The oxygen in-diffusion flow shows simple relaxation type behaviour J=J 0 exp( {-t}/{τ}) despite a rather broad particle size distribution. At higher temperatures, τ is activated with activation energies 0.55 and 0.25 eV in the tetragonal and orthorhombic phases, respectively. Comparison between twin-domain sizes and bulk oxygen in-diffusion time constants indicates that the twin-domain boundaries may contribute to the effective bulk oxygen in-diffusion. All our results may be interpreted in terms of the 2D ASYNNNI model description of the oxygen basal plane ordering, and they suggest that recent first principles interaction parameters should be modified.

A technique for measuring oxygen saturation in biological tissues based on diffuse optical spectroscopy

Science.gov (United States)

Kleshnin, Mikhail; Orlova, Anna; Kirillin, Mikhail; Golubiatnikov, German; Turchin, Ilya

2017-07-01

A new approach to optical measuring blood oxygen saturation was developed and implemented. This technique is based on an original three-stage algorithm for reconstructing the relative concentration of biological chromophores (hemoglobin, water, lipids) from the measured spectra of diffusely scattered light at different distances from the probing radiation source. The numerical experiments and approbation of the proposed technique on a biological phantom have shown the high reconstruction accuracy and the possibility of correct calculation of hemoglobin oxygenation in the presence of additive noise and calibration errors. The obtained results of animal studies have agreed with the previously published results of other research groups and demonstrated the possibility to apply the developed technique to monitor oxygen saturation in tumor tissue.

Limiting Current of Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells

DEFF Research Database (Denmark)

Li, Qingfeng; Gang, Xiao; Hjuler, Hans Aage

1994-01-01

on polytetrafluorine-ethyl bonded gas-diffusion electordes in phosphoric acid with and without fluorinated additives. This provides an alternative to estimate the film thickness by combining it with the acid-adsorption measurements and the porosity analysis of the catalyst layer. It was noticed that the limiting......Various models have been devoted to the operation mechanism of porous diffusion electrodes. They are, however, suffering from the lack of accuracy concerning the acid-film thickness on which they are based. In the present paper the limiting current density has been measured for oxygen reduction...... current density can be accomplished either by gas-phase diffusion or liquid-phase diffusion, and it is the latter that can be used in the film-thickness estimation. It is also important to mention that at such a limiting condition, both the thin-film model and the filmed agglomerate model reach the same...

Effect of hypolimnetic oxygenation on oxygen depletion rates in two water-supply reservoirs.

Science.gov (United States)

Gantzer, Paul A; Bryant, Lee D; Little, John C

2009-04-01

Oxygenation systems, such as bubble-plume diffusers, are used to improve water quality by replenishing dissolved oxygen (DO) in the hypolimnia of water-supply reservoirs. The diffusers induce circulation and mixing, which helps distribute DO throughout the hypolimnion. Mixing, however, has also been observed to increase hypolimnetic oxygen demand (HOD) during system operation, thus accelerating oxygen depletion. Two water-supply reservoirs (Spring Hollow Reservoir (SHR) and Carvins Cove Reservoir (CCR)) that employ linear bubble-plume diffusers were studied to quantify diffuser effects on HOD. A recently validated plume model was used to predict oxygen addition rates. The results were used together with observed oxygen accumulation rates to evaluate HOD over a wide range of applied gas flow rates. Plume-induced mixing correlated well with applied gas flow rate and was observed to increase HOD. Linear relationships between applied gas flow rate and HOD were found for both SHR and CCR. HOD was also observed to be independent of bulk hypolimnion oxygen concentration, indicating that HOD is controlled by induced mixing. Despite transient increases in HOD, oxygenation caused an overall decrease in background HOD, as well as a decrease in induced HOD during diffuser operation, over several years. This suggests that the residual or background oxygen demand decreases from one year to the next. Despite diffuser-induced increases in HOD, hypolimnetic oxygenation remains a viable method for replenishing DO in thermally-stratified water-supply reservoirs such as SHR and CCR.

Terrestrial Fe-oxide Concretions and Mars Blueberries: Comparisons of Similar Advective and Diffusive Chemical Infiltration Reaction Mechanisms

Science.gov (United States)

Park, A. J.; Chan, M. A.

2006-12-01

Abundant iron oxide concretions occurring in Navajo Sandstone of southern Utah and those discovered at Meridiani Planum, Mars share many common observable physical traits such as their spheriodal shapes, occurrence, and distribution patterns in sediments. Terrestrial concretions are products of interaction between oxygen-rich aquifer water and basin-derived reducing (iron-rich) water. Water-rock interaction simulations show that diffusion of oxygen and iron supplied by slow-moving water is a reasonable mechanism for producing observed concretion patterns. In short, southern Utah iron oxide concretions are results of Liesegang-type diffusive infiltration reactions in sediments. We propose that the formation of blueberry hematite concretions in Mars sediments followed a similar diagenetic mechanism where iron was derived from the alteration of volcanic substrate and oxygen was provided by the early Martian atmosphere. Although the terrestrial analog differs in the original host rock composition, both the terrestrial and Mars iron-oxide precipitation mechanisms utilize iron and oxygen interactions in sedimentary host rock with diffusive infiltration of solutes from two opposite sources. For the terrestrial model, slow advection of iron-rich water is an important factor that allowed pervasive and in places massive precipitation of iron-oxide concretions. In Mars, evaporative flux of water at the top of the sediment column may have produced a slow advective mass-transfer mechanism that provided a steady source and the right quantity of iron. The similarities of the terrestrial and Martian systems are demonstrated using a water-rock interaction simulator Sym.8, initially in one-dimensional systems. Boundary conditions such as oxygen content of water, partial pressure of oxygen, and supply rate of iron were varied. The results demonstrate the importance of slow advection of water and diffusive processes for producing diagenetic iron oxide concretions.

Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes.

Science.gov (United States)

Neale, Alex R; Li, Peilin; Jacquemin, Johan; Goodrich, Peter; Ball, Sarah C; Compton, Richard G; Hardacre, Christopher

2016-04-28

This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in different ILs. The viscosity of the ILs and the calculated molar volume and free volume are also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying that oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of an ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas.

Diffusion in plasma: The Hall effect, compositional waves, and chemical spots

Energy Technology Data Exchange (ETDEWEB)

Urpin, V., E-mail: Vadim.urpin@uv.es [Ioffe Institute of Physics and Technology (Russian Federation)

2017-03-15

Diffusion caused by a combined influence of the electric current and Hall effect is considered, and it is argued that such diffusion can form inhomogeneities of a chemical composition in plasma. The considered mechanism can be responsible for the formation of element spots in laboratory and astrophysical plasmas. This current-driven diffusion can be accompanied by propagation of a particular type of waves in which the impurity number density oscillates alone. These compositional waves exist if the magnetic pressure in plasma is much greater than the gas pressure.

Oxygen diffusion and reactivity at low temperature on bare amorphous olivine-type silicate

Energy Technology Data Exchange (ETDEWEB)

Minissale, M., E-mail: marco.minissale@obspm.fr; Congiu, E.; Dulieu, F. [LERMA-LAMAp, Université de Cergy-Pontoise, Observatoire de Paris, ENS, UPMC, UMR 8112 du CNRS, 5 Mail Gay Lussac, 95000 Cergy Pontoise Cedex (France)

2014-02-21

The mobility of O atoms at very low temperatures is not generally taken into account, despite O diffusion would add to a series of processes leading to the observed rich molecular diversity in space. We present a study of the mobility and reactivity of O atoms on an amorphous silicate surface. Our results are in the form of reflection absorption infrared spectroscopy and temperature-programmed desorption spectra of O{sub 2} and O{sub 3} produced via two pathways: O + O and O{sub 2} + O, investigated in a submonolayer regime and in the range of temperature between 6.5 and 30 K. All the experiments show that ozone is formed efficiently on silicate at any surface temperature between 6.5 and 30 K. The derived upper limit for the activation barriers of O + O and O{sub 2} + O reactions is ∼150 K/k{sub b}. Ozone formation at low temperatures indicates that fast diffusion of O atoms is at play even at 6.5 K. Through a series of rate equations included in our model, we also address the reaction mechanisms and show that neither the Eley–Rideal nor the hot atom mechanisms alone can explain the experimental values. The rate of diffusion of O atoms, based on modeling results, is much higher than the one generally expected, and the diffusive process proceeds via the Langmuir-Hinshelwood mechanism enhanced by tunnelling. In fact, quantum effects turn out to be a key factor that cannot be neglected in our simulations. Astrophysically, efficient O{sub 3} formation on interstellar dust grains would imply the presence of huge reservoirs of oxygen atoms. Since O{sub 3} is a reservoir of elementary oxygen, and also of OH via its hydrogenation, it could explain the observed concomitance of CO{sub 2} and H{sub 2}O in the ices.

Chemical reaction of atomic oxygen with evaporated films of copper, part 4

Science.gov (United States)

Fromhold, A. T.; Williams, J. R.

1990-01-01

Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

Science.gov (United States)

Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

2018-03-01

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

Chemical complexity in the winds of the oxygen-rich supergiant star VY Canis Majoris

Science.gov (United States)

Ziurys, L. M.; Milam, S. N.; Apponi, A. J.; Woolf, N. J.

2007-06-01

The interstellar medium is enriched primarily by matter ejected from old, evolved stars. The outflows from these stars create spherical envelopes, which foster gas-phase chemistry. The chemical complexity in circumstellar shells was originally thought to be dominated by the elemental carbon to oxygen ratio. Observations have suggested that envelopes with more carbon than oxygen have a significantly greater abundance of molecules than their oxygen-rich analogues. Here we report observations of molecules in the oxygen-rich shell of the red supergiant star VY Canis Majoris (VY CMa). A variety of unexpected chemical compounds have been identified, including NaCl, PN, HNC and HCO+. From the spectral line profiles, the molecules can be distinguished as arising from three distinct kinematic regions: a spherical outflow, a tightly collimated, blue-shifted expansion, and a directed, red-shifted flow. Certain species (SiO, PN and NaCl) exclusively trace the spherical flow, whereas HNC and sulphur-bearing molecules (amongst others) are selectively created in the two expansions, perhaps arising from shock waves. CO, HCN, CS and HCO+ exist in all three components. Despite the oxygen-rich environment, HCN seems to be as abundant as CO. These results suggest that oxygen-rich shells may be as chemically diverse as their carbon counterparts.

Chemical diffusion of Cr, Ni and Si in welded joints. II

International Nuclear Information System (INIS)

Kucera, J.; Ciha, K.

1987-01-01

The results are given of a study in chemical diffusion in welded joints P2/A and P3/A. P2 stands for the steel (Fe-17.48 Cr-8.15 Ni-0.14 Si), P3 for (Fe-18.52 Cr-8.20 Ni-1.78 Si) and A for the Fe-Arema. Triadic sandwiche-like samples were diffusion heated at temperatures from 920 to 1170 degC. The concentration distributions N(x,t) of the given elements were measured with microprobe JXA-3A. The evaluation of the experimental data was carried out either by Grube's method, or in some cases by the spline-polynomial method. The evaluated diffusivities D-bar satisfy the Arrhenius relation and yield the standard diffusion characteristics D 0 and H. The diffusivities D-bar of Cr, Ni and Si in P1/A, in P2/A and P3/A welded joints vary with Si content in P1, P2 and P3 alloys, similar to the Cr-51 and Ni-63 self-diffusivities in Fe-18 Cr-12 Ni-X Si steels, and tend to increase with increasing Si content. The values D-bar measured in the vicinity of grain boundaries are higher than the bulk diffusion coefficients. The most rapid diffusant is Si and the slowest one Ni. Thus, the relations D-bar Si :D-bar Cr :D-bar Ni ≅ 6:3:1 (P3/A) and D-bar Si :D-bar Cr :D-bar Ni ≅ 1.7:1.4:1 (P3/A) are valid at 1050 degC. Comparing the results with those published if can be noted that the Cr-51 and Ni-63 self-diffusion in Fe-18 Cr-12 Ni-X Si steels is faster than chemical diffusion of these elements in the said steel welded joints P2/A and P3/A; X varies from 0.14 to 1.98. (author). 7 tabs., 7 figs., 20 refs

The chemical evolution of white dwarf atmospheres: Diffusion and accretion

International Nuclear Information System (INIS)

Vauclair, G.; Vauclair, S.; Greenstein, J.L.

1979-01-01

A study of diffusion processes in white dwarfs is presented. We are especially interested in the estimate of the diffusion time scales for C, N, O, Mg, and Ca along the cooling sequence. The effect of the radiative acceleration is important in hot white dwarfs while in cooler ones the thermal diffusion dominates the gravitational settling. In hot white dwarfs, there should be an observable amount of CNO elements unless they have previously left the stars by a selective wind. Observational tests of this result are discussed. The diffusion time scales are always short compared to the evolutionary time scales. It is shown that in both hydrogen and helium envelopes, the convection zone, even at its maximum depth, is not able to bring back to the stellar surface the metals which have previously diffused downwards. The diffusion alone predicts a complete absence of metals in white dwarf atmospheres and envelopes. As metals are observed in white dwarfs, at least at effective temperatures lower than 15,000 K, there must be some mechanism competing with diffusion. We investigate the competition between diffusion and accretion and propose a general scheme for the chemical evolution of white dwarf atmospheres along the cooling sequence. (orig.)

Singlet oxygen generator for a solar powered chemically pumped iodine laser

Science.gov (United States)

Busch, G. E.

1984-01-01

The potential of solid phase endoperoxides as a means to produce single-delta oxygen in the gas phase in concentrations useful to chemical oxygen-iodine lasers was investigated. The 1,4 - endoperoxide of ethyl 3- (4-methyl - 1-naphthyl) propanoate was deposited over an indium-oxide layer on a glass plate. Single-delta oxygen was released from the endoperoxide upon heating the organic film by means of an electrical discharge through the conductive indium oxide coating. The evolution of singlet-delta oxygen was determined by measuring the dimol emission signal at 634 nm. Comparison of the measured signal with an analytic model leads to two main conclusions: virtually all the oxygen being evolved is in the singlet-delta state and in the gas phase, and there is no significant quenching other than energy pooling on the time scale of the experiment (approximately 10 msec). The use of solid phase endoperoxide as a singlet-delta oxygen generator for an oxygen-iodine laser appears promising.

Metal ferrite oxygen carriers for chemical looping combustion of solid fuels

Science.gov (United States)

Siriwardane, Ranjani V.; Fan, Yueying

2017-01-31

The disclosure provides a metal ferrite oxygen carrier for the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The metal ferrite oxygen carrier comprises MFe.sub.xO.sub.y on an inert support, where MFe.sub.xO.sub.y is a chemical composition and M is one of Mg, Ca, Sr, Ba, Co, Mn, and combinations thereof. For example, MFe.sub.xO.sub.y may be one of MgFe.sub.2O.sub.4, CaFe.sub.2O.sub.4, SrFe.sub.2O.sub.4, BaFe.sub.2O.sub.4, CoFe.sub.2O.sub.4, MnFeO.sub.3, and combinations thereof. The MFe.sub.xO.sub.y is supported on an inert support. The inert support disperses the MFe.sub.xO.sub.y oxides to avoid agglomeration and improve performance stability. In an embodiment, the inert support comprises from about 5 wt. % to about 60 wt. % of the metal ferrite oxygen carrier and the MFe.sub.xO.sub.y comprises at least 30 wt. % of the metal ferrite oxygen carrier. The metal ferrite oxygen carriers disclosed display improved reduction rates over Fe.sub.2O.sub.3, and improved oxidation rates over CuO.

Syngas Generation from Methane Using a Chemical-Looping Concept: A Review of Oxygen Carriers

Directory of Open Access Journals (Sweden)

Kongzhai Li

2013-01-01

Full Text Available Conversion of methane to syngas using a chemical-looping concept is a novel method for syngas generation. This process is based on the transfer of gaseous oxygen source to fuel (e.g., methane by means of a cycling process using solid oxides as oxygen carriers to avoid direct contact between fuel and gaseous oxygen. Syngas is produced through the gas-solid reaction between methane and solid oxides (oxygen carriers, and then the reduced oxygen carriers can be regenerated by a gaseous oxidant, such as air or water. The oxygen carrier is recycled between the two steps, and the syngas with a ratio of H2/CO = 2.0 can be obtained successively. Air is used instead of pure oxygen allowing considerable cost savings, and the separation of fuel from the gaseous oxidant avoids the risk of explosion and the dilution of product gas with nitrogen. The design and elaboration of suitable oxygen carriers is a key issue to optimize this method. As one of the most interesting oxygen storage materials, ceria-based and perovskite oxides were paid much attention for this process. This paper briefly introduced the recent research progresses on the oxygen carriers used in the chemical-looping selective oxidation of methane (CLSOM to syngas.

Impact of the structural anisotropy of La2NiO4+δ on on high temperature surface modifications and diffusion of oxygen

International Nuclear Information System (INIS)

Gauquelin, Nicolas

2010-01-01

La 2 NiO 4+δ was first studied due to its structural similarities with the High Temperature superconductor La 2 NiO 4+δ and more recently due to its promise as a cathode material in Solid Oxide Fuel Cells as well as an oxygen exchange membrane. It crystallizes in the K 2 NiF 4 layered structure and accommodates highly mobile oxygen at its ground state and is therefore overstoichiometric. During this thesis, pure single crystals of La 2 NiO 4+δ were successfully grown using the floating-zone method, subsequently characterized using neutron and Laue Backscattering diffraction and oriented pieces of single crystal with [100] and [001] orientation were prepared. The surface morphology behavior after long term exposure to high temperature in different atmospheres was observed using microscopy techniques because stability at high temperature is required for application purposes and it was discovered a structural change to nickel-rich phases at T>1173 K. The sensibility of the oxygen non-stoichiometry to cooling was studied and subsequently a new 18 O- 18 O exchange apparatus allowing quenching of the samples using liquid nitrogen was developed. Oxygen selfdiffusion was studied using SIMS in the range 673-873K in both [100] and [001] crystallographic directions. The effect of the disorientation of the sample surface on the determination of the slowest diffusion coefficient was discovered and revealed the very strong anisotropy (>5 orders of magnitude difference) between the different diffusion paths. Finally using HTXRD and oxygen release experiments, it was shown that oxygen diffusion from interstitial oxygen starts to be relevant at 550-600 K and a change of behavior is observed around 700 K, corresponding to a possible change in the diffusion mechanism from interstitial to interstitialcy.

The effects of a stress field and chemical diffusion on electronic behaviour in InAs/GaAs quantum dots

International Nuclear Information System (INIS)

Zhang Xu; Wang Chongyu

2006-01-01

The effects of a stress field and chemical diffusion on electronic behaviour in self-assembled InAs/GaAs quantum dots (QD) are investigated by using first-principle calculations. We find that a potential well appears in a QD without a lattice misfit and chemical diffusion, and both stress field and Ga chemical diffusion can induce the formation of a potential barrier, which strongly affects the electronic behaviour within the QD. The stress field can localize electrons to the base of the QD. And associated with Ga diffusion, the stress field will induce an inverted electronic alignment. The electronic behaviour in the QD without a stress field does not present the confined or localized characteristics caused by a lattice misfit, atomic size and Ga diffusion. This study provides useful information for modulating electronic behaviour by introducing a stress field and chemical diffusion

Electrochemical study on determination of diffusivity, activity and solubility of oxygen in liquid bismuth

Energy Technology Data Exchange (ETDEWEB)

Ganesan, Rajesh [Liquid Metals and Structural Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Gnanasekaran, T. [Liquid Metals and Structural Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India)]. E-mail: gnani@igcar.ernet.in; Srinivasa, Raman S. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400 076 (India)

2006-06-15

Diffusivity of oxygen in liquid bismuth was measured by potentiostatic method and is given bylg(D{sub O}{sup Bi}/cm{sup 2}.s{sup -1})(+/-0.042)=-3.706-1377/(TK{sup -1})(804oxygen in bismuth was determined by coulometric titrations and using the measured data standard free energy of dissolution of oxygen in liquid bismuth was derived for the reaction:1/2O{sub 2}(g)=[O]{sub Bi}(at.%)and is given by{delta}G{sub O(Bi)}{sup o}/(J.g-atomO{sup -1})(+/-720)=-108784+20.356TK{sup -1}(753oxygen in liquid bismuth was derived as a function of temperature and is given by the following expressions:lg(S/at%O)(+/-0.05)=-4476/TK{sup -1}+4.05(753oxygen in liquid bismuth is compared with the literature data.

Kinetics of oxygen uncoupling of a copper based oxygen carrier

International Nuclear Information System (INIS)

Hu, Wenting; Donat, Felix; Scott, S.A.; Dennis, J.S.

2016-01-01

Highlights: • The kinetics of a Cu-based oxygen carrier was determined using a TGA. • A diffusion model was applied to remove mass transfer effects from rate parameters. • Thermodynamics are separated from kinetics, usually difficult for the CLOU reaction. • The rate parameters correctly described the behaviour in a fluidised bed. • The rate parameters can be used to predict performance of large CLOU systems. - Abstract: Here, an oxygen carrier consisting of 60 wt% CuO supported on a mixture of Al_2O_3 and CaO (23 wt% and 17 wt% respectively) was synthesised by wet-mixing powdered CuO, Al(OH)_3 and Ca(OH)_2, followed by calcination at 1000 °C. Its suitability for chemical looping with oxygen uncoupling (CLOU) was investigated. After 25 repeated redox cycles in either a thermogravimetric analyser (TGA) or a laboratory-scale fluidised bed, (with 5 vol% H_2 in N_2 as the fuel, and air as the oxidant) no significant change in either the oxygen uncoupling capacity or the overall oxygen availability of the carrier was found. In the TGA, it was found that the rate of oxygen release from the material was controlled by intrinsic chemical kinetics and external transfer of mass from the surface of the particles to the bulk gas. By modelling the various resistances, values of the rate constant for the decomposition were obtained. The activation energy of the reaction was found to be 59.7 kJ/mol (with a standard error of 5.6 kJ/mol) and the corresponding pre-exponential factor was 632 m"3/mol/s. The local rate of conversion within a particle was assumed to occur either (i) by homogeneous chemical reaction, or (ii) in uniform, non-porous grains, each reacting as a kinetically-controlled shrinking core. Upon cross validation against a batch fluidised bed experiment, the homogeneous reaction model was found to be more plausible. By accurately accounting for the various artefacts (e.g. mass transfer resistances) present in both TGA and fluidised bed experiments, it was

An Electrochemical Investigation of the Chemical Diffusivity in Liquid Metal Alloys

Science.gov (United States)

Barriga, Salvador A.

The liquid metal battery has been shown to be a viable candidate for grid-scale energy storage, due to its fast kinetics and ability to be constructed from economically feasible materials. Various of the liquid metal couples that form high stable voltages, such as the calcium chemistries, are rate limited because they tend to form solid intermetallic compounds with high melting points. In order to understand and better engineer these batteries, the kinetic properties of these liquid alloys, in particular the chemical diffusivity, must be known accurately so that it can be used as input in computational simulations to avoid the nucleation of any solids. Unfortunately, the dominant experimental methods for measuring diffusion in liquid metals today are unreliable because the measurement timescales are on the order of days, require long capillaries susceptible to buoyancy-driven flow from temperature fluctuations, and composition analysis must be done ex-situ as a solid. To counter all these problems, a new and novel method for measuring the chemical diffusivity of metals in liquid alloys derived from electrochemical principles is presented in this thesis. This new method has the advantage of operating in shorter times scales of minutes rather than days, and requires the use of small capillaries which collectively minimize the effect of convectively-driven flow caused from temperature gradients. This new method was derived by solving the same boundary conditions required by the galvanostatic intermittent titration technique for solid-state electrodes. To verify the validity of the new theoretical derivation, the method was used to measure the chemical diffusivity of calcium in liquid bismuth within the temperature range of 550 - 700 °C using a three-electrode setup with a ternary molten salt electrolyte. Three compositions where studied (5% Ca-Bi, 10% Ca-Bi, and 15% Ca-Bi) for comparison. The chemical diffusion coefficient was found to range between (6.77 +/- 0.21)x

Oxygen permeation and thermo-chemical stability of oxygen separation membrane materials for the oxyfuel process

Energy Technology Data Exchange (ETDEWEB)

Ellett, Anna Judith

2009-07-01

The reduction of CO{sub 2} emissions, generally held to be one of the most significant contributors to global warming, is a major technological issue. CO{sub 2} Capture and Storage (CCS) techniques applied to large stationary sources such as coal-fired power plants could efficiently contribute to the global carbon mitigation effort. The oxyfuel process, which consists in the burning of coal in an oxygen-rich atmosphere to produce a flue gas highly concentrated in CO{sub 2}, is a technology considered for zero CO{sub 2} emission coal-fired power plants. The production of this O{sub 2}-rich combustion gas from air can be carried out using high purity oxygen separation membranes. Some of the most promising materials for this application are mixed ionic-electronic conducting (MIEC) materials with perovskite and K{sub 2}NiF{sub 4} perovskite-related structures. The present work examines the selection of La{sub 0.58}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{delta}} (LSCF58), La{sub 2}NiO{sub 4+{delta}}, Pr{sub 0.58}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{delta}} (PSCF58) and Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (BSCF50) as membrane materials for the separation of O{sub 2} and N{sub 2} in the framework of the oxyfuel process with flue gas recycling. Annealing experiments were carried out on pellets exposed to CO{sub 2}, water vapour, O{sub 2} and Cr{sub 2}O{sub 3} in order to determine the thermo-chemical resistance to the atmospheres and the high temperature conditions present during membrane operation in a coal-fired power plant. The degradation of their microstructure was investigated using Scanning Electron Microscopy (SEM) in combination with electron dispersive spectroscopy (EDS) as well as X-Ray Diffraction (XRD). Also, the oxygen permeation fluxes of selected membranes were investigated as a function of temperature. The membrane materials selected were characterised using thermo-analytical techniques such as precision thermogravimetric

Differences in spirometry and diffusing capacity after a 3-h wet or dry oxygen dive with a PO(2) of 150 kPa

NARCIS (Netherlands)

van Ooij, P. J. A. M.; van Hulst, R. A.; Houtkooper, A.; Sterk, P. J.

2011-01-01

Breathing oxygen with a partial pressure of >50 kPa causes pulmonary oxygen toxicity (POT), resulting in a decrease in vital capacity (VC) and in diffusing capacity for carbon monoxide (DLco). As submersion is thought to potentiate POT, we hypothesized that submerged oxygen divers are at increased

Chemically mediated diffusion of d-metals and B through Si and agglomeration at Si-on-Mo interfaces

NARCIS (Netherlands)

T. Tsarfati,; Zoethout, E.; van de Kruijs, R.; F. Bijkerk,

2009-01-01

Chemical diffusion and interlayer formation in thin layers and at interfaces is of increasing influence in nanoscopic devices, such as nanoelectronics and reflective multilayer optics. Chemical diffusion and agglomeration at interfaces of thin Ru, Mo, Si, and B4C layers have been studied with x-ray

Influence of the oxygen electrode and inter-diffusion barrier on the degradation of solid oxide electrolysis cells

DEFF Research Database (Denmark)

Hjalmarsson, Per; Sun, Xiufu; Liu, Yi-Lin

2013-01-01

-diffusion barrier sandwiched between the YSZ electrolyte and an LSCF:CGO oxygen electrode. Impedance Spectroscopy was used during the tests to diagnose the change in electrochemical response of the different components of the SOECs. The results showed a significantly lower degradation rate for the cell with an LSCF......Two Solid Oxide Electrolysis Cells (SOECs) with different oxygen electrodes have been tested in galvanostatic tests carried out at −1.5 Acm−2 and 800 °C converting 60% of a 50:50% mixture of H2O and CO2 (co-electrolysis). One of the cells had an LSM:YSZ oxygen electrode. The other had an CGO inter...

Oxygen Barrier Coating Deposited by Novel Plasma-enhanced Chemical Vapor Deposition

DEFF Research Database (Denmark)

Jiang, Juan; Benter, M.; Taboryski, Rafael Jozef

2010-01-01

We report the use of a novel plasma-enhanced chemical vapor deposition chamber with coaxial electrode geometry for the SiOx deposition. This novel plasma setup exploits the diffusion of electrons through the inner most electrode to the interior samples space as the major energy source. This confi......We report the use of a novel plasma-enhanced chemical vapor deposition chamber with coaxial electrode geometry for the SiOx deposition. This novel plasma setup exploits the diffusion of electrons through the inner most electrode to the interior samples space as the major energy source...... effect of single-layer coatings deposited under different reaction conditions was studied. The coating thickness and the carbon content in the coatings were found to be the critical parameters for the barrier property. The novel barrier coating was applied on different polymeric materials...

Oxygen transport in La0.6Sr0.4Co1-yFeyO3-d

NARCIS (Netherlands)

Bouwmeester, Henricus J.M.; den Otter, M.W.; Boukamp, Bernard A.

2004-01-01

The surface exchange coefficient and chemical diffusion coefficient of oxygen for the perovskites La0.6Sr0.4Co1–yFeyO3–delta (y=0.2, 0.5 and 0.8) were measured using the conductivity relaxation technique. Measurements were performed between 600 and 800 °C in an oxygen partial pressure range between

Morphological Pulmonary Diffusion Capacity for Oxygen of Burmese Pythons (Python molurus): a Comparison of Animals in Healthy Condition and with Different Pulmonary Infections.

Science.gov (United States)

Starck, J M; Weimer, I; Aupperle, H; Müller, K; Marschang, R E; Kiefer, I; Pees, M

2015-11-01

A qualitative and quantitative morphological study of the pulmonary exchange capacity of healthy and diseased Burmese pythons (Python molurus) was carried out in order to test the hypothesis that the high morphological excess capacity for oxygen exchange in the lungs of these snakes is one of the reasons why pathological processes extend throughout the lung parenchyma and impair major parts of the lungs before clinical signs of respiratory disease become apparent. Twenty-four Burmese pythons (12 healthy and 12 diseased) were included in the study. A stereology-based approach was used to quantify the lung parenchyma using computed tomography. Light microscopy was used to quantify tissue compartments and the respiratory exchange surface, and transmission electron microscopy was used to measure the thickness of the diffusion barrier. The morphological diffusion capacity for oxygen of the lungs and the anatomical diffusion factor were calculated. The calculated anatomical diffusion capacity was compared with published values for oxygen consumption of healthy snakes, and the degree to which the exchange capacity can be obstructed before normal physiological function is impaired was estimated. Heterogeneous pulmonary infections result in graded morphological transformations of pulmonary parenchyma involving lymphocyte migration into the connective tissue and thickening of the septal connective tissue, increasing thickness of the diffusion barrier and increasing transformation of the pulmonary epithelium into a columnar pseudostratified or stratified epithelium. The transformed epithelium developed by hyperplasia of ciliated cells arising from the tip of the faveolar septa and by hyperplasia of type II pneumocytes. These results support the idea that the lungs have a remarkable overcapacity for oxygen consumption and that the development of pulmonary disease continuously reduces the capacity for oxygen consumption. However, due to the overcapacity of the lungs, this

Oxygen diffusion in Y sub 1 sub - sub x Pr sub x Ba sub 2 Cu sub 3 O sub 7 sub - subdelta observed by resistivity measurements

CERN Document Server

Diosa, J E; Mellander, B E

1997-01-01

In situ resistivity measurements have been used to monitor the oxygen uptake and removal for the ceramic system Y sub 1 sub - sub x Pr sub x Ba sub 2 Cu sub 3 O sub 7 sub - subdelta (YPBCO) in the temperature range 300 - 1000 K. The study of the out-diffusion of oxygen was performed by annealing the oxygenated samples in ambient air at constant heating rates. We found that, independently of x, the oxygen concentration O sub 7 sub - subdelta is preserved up to 600 K, and that oxygen diffuses out of the oxides at temperatures higher than 600 K. However, the rate of oxygen removal from PrBa sub 2 Cu sub 3 O sub 7 sub - subdelta (PBCO) is greatly reduced as compared to the rate for pure YBa sub 2 Cu sub 3 O sub 7 sub - subdelta (YBCO), and decreases with increasing x in YPBCO. The study of the in-diffusion of oxygen was performed by annealing the deoxygenated samples in ambient air at constant heating rates. We found that, independently of x, the oxygen uptake takes place in the temperature range 550 - 750 K, whe...

Innovative oxide materials for electrochemical energy conversion and oxygen separation

Science.gov (United States)

Belousov, V. V.

2017-10-01

Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion

Energy Technology Data Exchange (ETDEWEB)

Nadarajah, Arunan [Univ. of Toledo, OH (United States)

2017-04-26

Among numerous methods of controlling the global warming effect, Chemical Looping Combustion is known to be the most viable option currently. A key factor to a successful chemical looping process is the presence of highly effective oxygen carriers that enable fuel combustion by going through oxidation and reduction in the presence of air and fuel respectively. In this study, CaMnO_3-δ was used as the base material and doped on the A-site (Sr or La) and B-site (Fe, Ti, Zn and Al) by 10 mol % of dopants. Solid state reaction followed by mechanical extrusion (optimized paste formula) was used as the preparation method A series of novel doped perovskite-type oxygen carrier particles (Ca_xLa (Or Sa)_1-x Mn_1-yByO_3-δ (B-site = Fe, Ti, Al, or Zr)) were synthesized by the proposed extrusion formula. The produced samples were characterized with XRD, SEM, BET and TGA techniques. According to the results obtained from TGA analysis, the oxygen capacity of the samples ranged between 1.2 for CLMZ and 1.75 for CSMF. Reactivity and oxygen uncoupling behaviors of the prepared samples were also evaluated using a fluidized bed chemical looping reactor using methane as the fuel at four different temperatures (800, 850, 900, 950 °C). All of the oxygen carriers showed oxygen uncoupling behavior and they were able to capture and release oxygen. Mass-based conversion of the perovskites was calculated and temperature increase proved to increase the mass-based conversion rate in all of the samples under study. Gas yield was calculated at 950 °C as well, and results showed that CLMZ, CM and CSMF showed 100% gas yields and CLMF and CSMZ showed approximately 85% yield in fluidized bed reactor, which is a high and acceptable quantity. Based on extended reactor tests the modified calcium manganese perovskite structures (CSMF) can be a good candidate for future pilot tests.

Regenerable mixed copper-iron-inert support oxygen carriers for solid fuel chemical looping combustion process

Energy Technology Data Exchange (ETDEWEB)

Siriwardane, Ranjani V.; Tian, Hanjing

2016-12-20

The disclosure provides an oxygen carrier for a chemical looping cycle, such as the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The oxygen carrier is comprised of at least 24 weight % (wt %) CuO, at least 10 wt % Fe2O3, and an inert support, and is typically a calcine. The oxygen carrier exhibits a CuO crystalline structure and an absence of iron oxide crystalline structures under XRD crystallography, and provides an improved and sustained combustion reactivity in the temperature range of 600.degree. C.-1000.degree. C. particularly for solid fuels such as carbon and coal.

Reaction-diffusion path planning in a hybrid chemical and cellular-automaton processor

International Nuclear Information System (INIS)

Adamatzky, Andrew; Lacy Costello, Benjamin de

2003-01-01

To find the shortest collision-free path in a room containing obstacles we designed a chemical processor and coupled it with a cellular-automaton processor. In the chemical processor obstacles are represented by sites of high concentration of potassium iodide and a planar substrate is saturated with palladium chloride. Potassium iodide diffuses into the substrate and reacts with palladium chloride. A dark coloured precipitate of palladium iodide is formed almost everywhere except sites where two or more diffusion wavefronts collide. The less coloured sites are situated at the furthest distance from obstacles. Thus, the chemical processor develops a repulsive field, generated by obstacles. A snapshot of the chemical processor is inputted to a cellular automaton. The automaton behaves like a discrete excitable media; also, every cell of the automaton is supplied with a pointer that shows an origin of the cell's excitation. The excitation spreads along the cells corresponding to precipitate depleted sites of the chemical processor. When the destination-site is excited, waves travel on the lattice and update the orientations of the pointers. Thus, the automaton constructs a spanning tree, made of pointers, that guides a traveler towards the destination point. Thus, the automaton medium generates an attractive field and combination of this attractive field with the repulsive field, generated by the chemical processor, provides us with a solution of the collision-free path problem

Chemical vapor deposition of refractory ternary nitrides for advanced diffusion barriers

Energy Technology Data Exchange (ETDEWEB)

Custer, Jonathan S.; Fleming, James G.; Roherty-Osmun, Elizabeth; Smith, Paul Martin

1998-09-22

Refractory ternary nitride films for diffusion barriers in microelectronics have been grown using chemical vapor deposition. Thin films of titanium-silicon-nitride, tungsten-boron-nitride, and tungsten-silicon-nitride of various compositions have been deposited on 150 mm Si wafers. The microstructure of the films are either fully amorphous for the tungsten based films, or nauocrystalline TiN in an amorphous matrix for titanium-silicon-nitride. All films exhibit step coverages suitable for use in future microelectronics generations. Selected films have been tested as diffusion barriers between copper and silicon, and generally perform extremely weH. These fiIms are promising candidates for advanced diffusion barriers for microelectronics applications. The manufacturing of silicon wafers into integrated circuits uses many different process and materials. The manufacturing process is usually divided into two parts: the front end of line (FEOL) and the back end of line (BEOL). In the FEOL the individual transistors that are the heart of an integrated circuit are made on the silicon wafer. The responsibility of the BEOL is to wire all the transistors together to make a complete circuit. The transistors are fabricated in the silicon itself. The wiring is made out of metal, currently aluminum and tungsten, insulated by silicon dioxide, see Figure 1. Unfortunately, silicon will diffuse into aluminum, causing aluminum spiking of junctions, killing transistors. Similarly, during chemical vapor deposition (CVD) of tungsten from ~fj, the reactivity of the fluorine can cause "worn-holes" in the silicon, also destroying transistors. The solution to these problems is a so-called diffusion barrier, which will allow current to pass from the transistors to the wiring, but will prevent reactions between silicon and the metal.

Impact of the structural anisotropy of La{sub 2}NiO{sub 4+δ} on on high temperature surface modifications and diffusion of oxygen

Energy Technology Data Exchange (ETDEWEB)

Gauquelin, Nicolas

2010-11-29

La{sub 2}NiO{sub 4+δ} was first studied due to its structural similarities with the High Temperature superconductor La{sub 2}NiO{sub 4+δ} and more recently due to its promise as a cathode material in Solid Oxide Fuel Cells as well as an oxygen exchange membrane. It crystallizes in the K{sub 2}NiF{sub 4} layered structure and accommodates highly mobile oxygen at its ground state and is therefore overstoichiometric. During this thesis, pure single crystals of La{sub 2}NiO{sub 4+δ} were successfully grown using the floating-zone method, subsequently characterized using neutron and Laue Backscattering diffraction and oriented pieces of single crystal with [100] and [001] orientation were prepared. The surface morphology behavior after long term exposure to high temperature in different atmospheres was observed using microscopy techniques because stability at high temperature is required for application purposes and it was discovered a structural change to nickel-rich phases at T>1173 K. The sensibility of the oxygen non-stoichiometry to cooling was studied and subsequently a new {sup 18}O-{sup 18}O exchange apparatus allowing quenching of the samples using liquid nitrogen was developed. Oxygen selfdiffusion was studied using SIMS in the range 673-873K in both [100] and [001] crystallographic directions. The effect of the disorientation of the sample surface on the determination of the slowest diffusion coefficient was discovered and revealed the very strong anisotropy (>5 orders of magnitude difference) between the different diffusion paths. Finally using HTXRD and oxygen release experiments, it was shown that oxygen diffusion from interstitial oxygen starts to be relevant at 550-600 K and a change of behavior is observed around 700 K, corresponding to a possible change in the diffusion mechanism from interstitial to interstitialcy.

Evolution of porosity and diffusivity associated with chemical weathering of a basalt clast

Energy Technology Data Exchange (ETDEWEB)

Navarre-Sitchler, A.; Steefel, C.I.; Yang, L.; Tomutsa, L.; Brantley, S.L.

2009-02-15

Weathering of rocks as a result of exposure to water and the atmosphere can cause significant changes in their chemistry and porosity. In low-porosity rocks, such as basalts, changes in porosity, resulting from chemical weathering, are likely to modify the rock's effective diffusivity and permeability, affecting the rate of solute transport and thus potentially the rate of overall weathering to the extent that transport is the rate limiting step. Changes in total porosity as a result of mineral dissolution and precipitation have typically been used to calculate effective diffusion coefficients through Archie's law for reactive transport simulations of chemical weathering, but this approach fails to account for unconnected porosity that does not contribute to transport. In this study, we combine synchrotron X-ray microcomputed tomography ({mu}CT) and laboratory and numerical diffusion experiments to examine changes in both total and effective porosity and effective diffusion coefficients across a weathering interface in a weathered basalt clast from Costa Rica. The {mu}CT data indicate that below a critical value of {approx}9%, the porosity is largely unconnected in the basalt clast. The {mu}CT data were further used to construct a numerical pore network model to determine upscaled, effective diffusivities as a function of total porosity (ranging from 3 to 30%) for comparison with diffusivities determined in laboratory tracer experiments. By using effective porosity as the scaling parameter and accounting for critical porosity, a model is developed that accurately predicts continuum-scale effective diffusivities across the weathering interface of the basalt clast.

Accurate and precise measurement of oxygen isotopic fractions and diffusion profiles by selective attenuation of secondary ions (SASI).

Science.gov (United States)

Téllez, Helena; Druce, John; Hong, Jong-Eun; Ishihara, Tatsumi; Kilner, John A

2015-03-03

The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices.

Chemical homogeneity in the Orion Association: Oxygen abundances of B stars

Directory of Open Access Journals (Sweden)

Lanz T.

2012-02-01

Full Text Available We present non-LTE oxygen abundances for a sample of B stars in the Orion association. The abundance calculations included non-LTE line formation and used fully blanketed non-LTE model atmospheres. The stellar parameters were the same as adopted in the previous study by Cunha & Lambert (1994. We find that the young Orion stars in this sample of 10 stars are described by a single oxygen abundance with an average value of A(O = 8.78 and a small dispersion of ±0.05, dex which is of the order of the uncertainties in the analysis. This average oxygen abundance compares well with the average oxygen abundance obtained previously in Cunha & Lambert (1994: A(O = 8.72 ± 0.13 although this earlier study, based upon non-blanketed model atmospheres in LTE, displayed larger scatter. Small scatter of chemical abundances in Orion B stars had also been found in our previous studies for neon and argon; all based on the same effective temperature scale. The derived oxygen abundance distribution for the Orion association compares well with other results for the oxygen abundance in the solar neighborhood.

Natural Ores as Oxygen Carriers in Chemical Looping Combustion

Energy Technology Data Exchange (ETDEWEB)

Tian, Hanjing; Siriwardane, Ranjani; Simonyi, Thomas; Poston, James

2013-08-01

Chemical looping combustion (CLC) is a combustion technology that utilizes oxygen from oxygen carriers (OC), such as metal oxides, instead of air to combust fuels. The use of natural minerals as oxygen carriers has advantages, such as lower cost and availability. Eight materials, based on copper or iron oxides, were selected for screening tests of CLC processes using coal and methane as fuels. Thermogravimetric experiments and bench-scale fixed-bed reactor tests were conducted to investigate the oxygen transfer capacity, reaction kinetics, and stability during cyclic reduction/oxidation reaction. Most natural minerals showed lower combustion capacity than pure CuO/Fe{sub 2}O{sub 3} due to low-concentrations of active oxide species in minerals. In coal CLC, chryscolla (Cu-based), magnetite, and limonite (Fe-based) demonstrated better reaction performances than other materials. The addition of steam improved the coal CLC performance when using natural ores because of the steam gasification of coal and the subsequent reaction of gaseous fuels with active oxide species in the natural ores. In methane CLC, chryscolla, hematite, and limonite demonstrated excellent reactivity and stability in 50-cycle thermogravimetric analysis tests. Fe{sub 2}O{sub 3}-based ores possess greater oxygen utilization but require an activation period before achieving full performance in methane CLC. Particle agglomeration issues associated with the application of natural ores in CLC processes were also studied by scanning electron microscopy (SEM).

A molecular dynamics study on the oxygen diffusion in doped fluorites: the effect of the dopant distribution

Energy Technology Data Exchange (ETDEWEB)

Tarancon, A. [M2E/XaRMAE/IREC, Department of Advanced Materials for Energy Applications, Catalonia Institute for Energy Research (IREC), Josep Pla 2, Torre 2, B2, 08019 Barcelona (Spain); Morata, A.; Peiro, F. [MIND/XaRMAE/IN2UB, Department of Electronics, University of Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Dezanneau, G. [Laboratoire Structures, Proprietes et Modelisation des Solides, Grande Voie des Vignes, Ecole Centrale Paris, F-92295 Chatenay-Malabry Cedex (France)

2011-02-15

The effect of the dopant distribution on the oxygen diffusion in doped fluorites typically used for solid oxide fuel cells electrolyte applications has been analysed by using molecular dynamics simulations. The oxygen mass transport in both yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria has been studied and compared in the range of temperatures between 1,159 and 1,959 K. A new methodology based on the analysis of local environments is used to describe the diffusion process at an atomic scale. Preferred vacancy migration pathways, most suitable conduction models, energy landscapes and jump efficiency have been detailed for each material. Finally, a particular case of non-random distribution of dopants in YSZ is presented in order to quantitatively evaluate the effect of the dopant pattern on the mass transport properties and the potential of the methodology developed here for understanding and foreseeing real configurations at the nanoscale. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Enhanced Oxygen Diffusion Within the Internal Oxidation Zone of Alloy 617 in Controlled Impurity Helium Environments from 1023 K to 1123 K (750 °C to 850 °C)

Science.gov (United States)

Gulsoy, Gokce; Was, Gary S.

2015-04-01

Alloy 617 was exposed to He-CO-CO2 environments with of either 9 or 1320 at temperatures from 1023 K to 1123 K (750 °C to 850 °C) to determine the oxygen diffusion coefficients within the internal oxidation zone of the alloy. The oxygen diffusion coefficients determined based on both intergranular and transgranular oxidation rates were several orders of magnitude greater than those reported in pure nickel and in nickel-based binary alloys, indicating that the rapid internal aluminum oxidation of Alloy 617 was primarily due to enhanced oxygen diffusion along the incoherent Al2O3-alloy interfaces. The range of activation energy values determined for oxygen diffusion associated with the intergranular aluminum oxidation was from 149.6 to 154.7 kJ/mol, and that associated with the transgranular aluminum oxidation was from 244.7 to 283.5 kJ/mol.

Atomically layer-by-layer diffusion of oxygen/hydrogen in highly epitaxial PrBaCo{sub 2}O{sub 5.5+δ} thin films

Energy Technology Data Exchange (ETDEWEB)

Bao, Shanyong; Xu, Xing; Enriquez, Erik; Mace, Brennan E.; Chen, Garry; Kelliher, Sean P.; Chen, Chonglin, E-mail: cl.chen@utsa.edu [Department of Physics and Astronomy, University of Texas, San Antonio, Texas 78249 (United States); Zhang, Yamei [Department of Physics, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003 (China); Whangbo, Myung-Hwan [North Carolina State University, Raleigh, North Carolina 27695-8204 (United States); Dong, Chuang; Zhang, Qinyu [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024 (China)

2015-12-14

Single-crystalline epitaxial thin films of PrBaCo{sub 2}O{sub 5.5+δ} (PrBCO) were prepared, and their resistance R(t) under a switching flow of oxidizing and reducing gases were measured as a function of the gas flow time t in the temperature range of 200–800 °C. During the oxidation cycle under O{sub 2}, the PrBCO films exhibit fast oscillations in their dR(t)/dt vs. t plots, which reflect the oxidation processes, Co{sup 2+}/Co{sup 3+} → Co{sup 3+} and Co{sup 3+} → Co{sup 3+}/Co{sup 4+}, that the Co atoms of PrBCO undergo. Each oscillation consists of two peaks, with larger and smaller peaks representing the oxygen/hydrogen diffusion through the (BaO)(CoO{sub 2})(PrO)(CoO{sub 2}) layers of PrBCO via the oxygen-vacancy-exchange mechanism. This finding paves a significant avenue for cathode materials operating in low-temperature solid-oxide-fuel-cell devices and for chemical sensors with wide range of operating temperature.

Depressurization accident analysis of MPBR by PBRSIM with chemical reaction model

International Nuclear Information System (INIS)

No, Hee Cheon; Kadak, A. C.

2002-01-01

The simple model for natural circulation is implemented into PBR S IM to provide air inlet velocity from the containment air space. For the friction and form loss only the pebble region is considered conservatively modeling laminar flow through a packed bed. For the chemical reaction model of PBR S IM the oxidation rate is determined as the minimum value of three mechanisms estimated at each time step: oxygen mass flow rate entering the bottom of the reflector, oxidation rate by kinetics, and oxygen mass flow rate arriving at the graphite surface by diffusion. Oxygen mass flux arriving at the graphite surface by diffusion is estimated based on energy-mass analogy. Two types of exothermic chemical reaction are considered: (C + zO 2 → xCO + yCO 2 ) and (2CO + O 2 2CO 2 ). The heterogeneous and homogeneous chemical reaction rates by kinetics are determined by INEEL and Bruno correlations, respectively. The instantaneous depressurization accident of MPBR is simulated using PBR S IM with chemical model. The air inlet velocity is initially rapidly dropped within 10 hr and reaches a saturation value of about 1.5cm/s. The oxidation rate by the diffusion process becomes lower than that by the chemical kinetics above 600K. The maximum pebble bed temperatures without and with chemical reaction reach the peak values of 1560 and 1617 .deg. C at 80 hr and 92 hr, respectively. As the averaged temperatures in the bottom reflector and the pebble bed regions increase with time, (C+1/2O2 ->CO) reaction becomes dominant over (C+O 2 →CO 2 ) reaction. Also, the CO generated by (C+1/2O 2 →CO) reaction will be consumed by (2CO+O 2 →2CO 2 ) reaction and the energy homogeneously generated by this CO depletion reaction becomes dominant over the heterogeneous reaction

A theoretical model for oxygen transport in skeletal muscle under conditions of high oxygen demand.

Science.gov (United States)

McGuire, B J; Secomb, T W

2001-11-01

Oxygen transport from capillaries to exercising skeletal muscle is studied by use of a Krogh-type cylinder model. The goal is to predict oxygen consumption under conditions of high demand, on the basis of a consideration of transport processes occurring at the microvascular level. Effects of the decline in oxygen content of blood flowing along capillaries, intravascular resistance to oxygen diffusion, and myoglobin-facilitated diffusion are included. Parameter values are based on human skeletal muscle. The dependence of oxygen consumption on oxygen demand, perfusion, and capillary density are examined. When demand is moderate, the tissue is well oxygenated and consumption is slightly less than demand. When demand is high, capillary oxygen content declines rapidly with axial distance and radial oxygen transport is limited by diffusion resistance within the capillary and the tissue. Under these conditions, much of the tissue is hypoxic, consumption is substantially less than demand, and consumption is strongly dependent on capillary density. Predicted consumption rates are comparable with experimentally observed maximal rates of oxygen consumption.

Structure, electronic properties, and oxygen incorporation/diffusion characteristics of the Σ 5 TiN(310)[001] tilt grain boundary

Science.gov (United States)

McKenna, Keith P.

2018-02-01

First principles calculations are employed to investigate the structure, electronic properties, and oxygen incorporation/diffusion characteristics of the Σ 5 TiN(310) tilt grain boundary with relevance to applications of polycrystalline TiN in microelectronics and protective coatings. We show that the grain boundary does not significantly modify electronic states near the Fermi energy but does induce an upward shift of up to 0.6 eV in a number of deeper occupied bands. We also show that oxygen is preferentially incorporated into the TiN grain boundary (GB) but must overcome relatively high activation energies for further diffusion. These predictions are consistent with the "stuffed barrier model" proposed to explain the good barrier characteristics of TiN. We also show that while the oxidizing power of TiN GBs is not sufficient to reduce HfO2 (a prototypical gate dielectric material), they can act as a scavenger for interstitial oxygen. Altogether, these results provide the much needed atomistic insights into the properties of a model GB in TiN and suggest a number of directions for future investigation.

Calculation of hydrogen and oxygen uptake in fuel rod cladding during severe accidents using the integral diffusion method -- Preliminary design report

International Nuclear Information System (INIS)

Siefken, L.J.

1999-01-01

Preliminary designs are described for models of hydrogen and oxygen uptake in fuel rod cladding during severe accidents. Calculation of the uptake involves the modeling of seven processes: (1) diffusion of oxygen from the bulk gas into the boundary layer at the external cladding surface, (2) diffusion from the boundary layer into the oxide layer, (3) diffusion from the inner surface of the oxide layer into the metallic part of the cladding, (4) uptake of hydrogen in the event that the cladding oxide layer is dissolved in a steam-starved region, (5) embrittlement of cladding due to hydrogen uptake, (6) cracking of cladding during quenching due to its embrittlement and (7) release of hydrogen from the cladding after cracking of the cladding. An integral diffusion method is described for calculating the diffusion processes in the cladding. Experimental results are presented that show a rapid uptake of hydrogen in the event of dissolution of the oxide layer and a rapid release of hydrogen in the event of cracking of the oxide layer. These experimental results are used as a basis for calculating the rate of hydrogen uptake and the rate of hydrogen release. The uptake of hydrogen is limited to the equilibrium solubility calculated by applying Sievert's law. The uptake of hydrogen is an exothermic reaction that accelerates the heatup of a fuel rod. An embrittlement criteria is described that accounts for hydrogen and oxygen concentration and the extent of oxidation. A design is described for implementing the models for hydrogen and oxygen uptake and cladding embrittlement into the programming framework of the SCDAP/RELAP5 code. A test matrix is described for assessing the impact of the proposed models on the calculated behavior of fuel rods in severe accident conditions. This report is a revision and reissue of the report entitled; ''Preliminary Design Report for Modeling of Hydrogen Uptake in Fuel Rod Cladding During Severe Accidents.''

Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

International Nuclear Information System (INIS)

Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

2015-01-01

Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

Experimental study of an oxygen-hydrogen diffusion flame laden with solid alumina particles; Etude experimentale d'une flamme de diffusion oxygene-hydrogene ensemencee en particules solides d'alumine

Energy Technology Data Exchange (ETDEWEB)

Labor, S.

2003-07-15

Monocrystalline sapphire microspheres are generated through the melting of alumina (AL{sub 2}O{sub 3}) particles in a flame. The alumina particles are injected in a very peculiar O{sub 2}/H{sub 2} confined diffusion flame as it is a downwards vertical flame having fuel in periphery of a central powdered oxygen jet. Quantitative measurements were carried out (ADL, PIV) and supplemented by a numerical study (N3S-Natur). (1) The laminar behavior of the isothermal conditions is kept through reactive flow. Therefore, particles will mainly collide due to speed gradients. (2) It has been shown that an axial particle will have a transit time int the high temperature zone very different to that of an off-line one. (3) The PIV date proved that the particle density was not homogeneous. (4) The hydrogen jet hardly influences the flame aerodynamic structure. Conversely, the central oxygen jet is at premium due to its effect on both the flame speed and temperature distribution. (author)

Hydrogen Oxidation on Gas Diffusion Electrodes for Phosphoric Acid Fuel Cells in the Presence of Carbon Monoxide and Oxygen

DEFF Research Database (Denmark)

Gang, Xiao; Li, Qingfeng; Hjuler, Hans Aage

1995-01-01

Hydrogen oxidation has been studied on a carbon-supported platinum gas diffusion electrode in a phosphoric acidelectrolyte in the presence of carbon monoxide and oxygen in the feed gas. The poisoning effect of carbon monoxide presentin the feed gas was measured in the temperature range from 80...... to 150°C. It was found that throughout the temperaturerange, the potential loss due to the CO poisoning can be reduced to a great extent by the injection of small amounts ofgaseous oxygen into the hydrogen gas containing carbon monoxide. By adding 5 volume percent (v/o) oxygen, an almost...

Method for the determination of oxygen consumption rates and diffusion coefficients in multicellular spheroids

OpenAIRE

Mueller-Klieser, W.

1984-01-01

A method has been developed for the quantitative evaluation of oxygen tension (PO2) distributions in multicellular spheroids measured with O2-sensitive microelectrodes. The experimental data showed that multicellular tumor spheroids in stirred growth media were characterized by a diffusion-depleted zone surrounding the spheroids. This zone was elicited by an unstirred layer of medium next to the spheroid leading to a continuous decrease in the PO2 values from the bulk medium towards the spher...

Chemical gating of epitaxial graphene through ultrathin oxide layers.

Science.gov (United States)

Larciprete, Rosanna; Lacovig, Paolo; Orlando, Fabrizio; Dalmiglio, Matteo; Omiciuolo, Luca; Baraldi, Alessandro; Lizzit, Silvano

2015-08-07

We achieved a controllable chemical gating of epitaxial graphene grown on metal substrates by exploiting the electrostatic polarization of ultrathin SiO2 layers synthesized below it. Intercalated oxygen diffusing through the SiO2 layer modifies the metal-oxide work function and hole dopes graphene. The graphene/oxide/metal heterostructure behaves as a gated plane capacitor with the in situ grown SiO2 layer acting as a homogeneous dielectric spacer, whose high capacity allows the Fermi level of graphene to be shifted by a few hundreds of meV when the oxygen coverage at the metal substrate is of the order of 0.5 monolayers. The hole doping can be finely tuned by controlling the amount of interfacial oxygen, as well as by adjusting the thickness of the oxide layer. After complete thermal desorption of oxygen the intrinsic doping of SiO2 supported graphene is evaluated in the absence of contaminants and adventitious adsorbates. The demonstration that the charge state of graphene can be changed by chemically modifying the buried oxide/metal interface hints at the possibility of tuning the level and sign of doping by the use of other intercalants capable of diffusing through the ultrathin porous dielectric and reach the interface with the metal.

Time evolution of dissolved oxygen and redox conditions in a HLW repository

International Nuclear Information System (INIS)

Wersin, P.; Spahiu, K.; Bruno, J.

1994-02-01

The evolution of oxygen in a HLW repository has been studied using presently available geochemical background information. The important processes affecting oxygen migration in the near-field include diffusion and oxidation of pyrite and dissolved Fe(II). The evaluation of time scales of oxygen decrease is carried out with 1. an analytical approach involving the coupling of diffusion and chemical reaction, 2. a numerical geochemical approach involving the application of a newly developed diffusion-extended version of the STEADYQL code. Both approaches yield consistent rates of oxygen decrease and indicate that oxidation of pyrite impurities in the clay is the dominant process. The results obtained fRom geochemical modelling are interpreted in terms of evolution of redox conditions. Moreover, a sensitivity analysis of the major geochemical and physical parameters is performed. These results indicate that the uncertainties associated with reactive pyrite surface area impose the overall uncertainties of prediction of time scales. Thus, the obtained time of decrease to 1% of initial O 2 concentrations range between 7 and 290 years. The elapsed time at which the transition to anoxic conditions occurs is estimated to be within the same time range. Additional experimental information on redox sensitive impurities in the envisioned buffer and backfill material would further constrain the evaluated time scales. 41 refs

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

Science.gov (United States)

Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

2017-05-17

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

A pulsed oxygen - iodine chemical laser excited by a longitudinal electric discharge

International Nuclear Information System (INIS)

Vagin, Nikolai P; Yuryshev, Nikolai N

2002-01-01

The dependence of the energy parameters of an oxygen - iodine chemical laser with a bulk generation of iodine atoms in a longitudinal electric discharge on the length of the discharge gap is studied for various discharge energies and voltages and various working mixture compositions (at constant oxygen and iodine pressures). Analyses of the results suggests that temperature effects account for a twofold decrease in the specific energy yield for the lasing initiated by a longitudinal electric discharge compared to the photolytic initiation. (lasers)

The oxygen effect and adaptive response of cells. Report 3. Simulation of respiratory oxygenation and oxygen permeability of cells

International Nuclear Information System (INIS)

Ehpshtejn, I.M.

1978-01-01

Variations in the oxygen concentration in extracellural [O 2 ] 0 and intracellular [Osub(2)]sub(i) media of cells small in size (d = 2 ] 0 - t-curves). It is shown that the Value of [Osub(2)]sub(i) may be expressed by four variants of its functional dependence: (a) on enzymic reaction of oxygen consumption, (b) on the order of reaction with respect to oxygen, (c) on physiological parameters of cells, and (d) on characteristic oxygen concentrations in the system. Items (c) and (d) are based on the postulated diffusion-kinetic model of oxygen consumption by an idealized cell of small size that consists of a drop of homogenous solution of the respiratory enzyme which is characterized by an equivalent Michaelis constant. The drop is enveloped in a uniform membrane that possesses a definite diffuse resistance to oxygen

On Medium Chemical Reaction in Diffusion-Based Molecular Communication: a Two-Way Relaying Example

OpenAIRE

Farahnak-Ghazani, Maryam; Aminian, Gholamali; Mirmohseni, Mahtab; Gohari, Amin; Nasiri-Kenari, Masoumeh

2016-01-01

Chemical reactions are a prominent feature of molecular communication (MC) systems, with no direct parallels in wireless communications. While chemical reactions may be used inside the transmitter nodes, receiver nodes or the communication medium, we focus on its utility in the medium in this paper. Such chemical reactions can be used to perform computation over the medium as molecules diffuse and react with each other (physical-layer computation). We propose the use of chemical reactions for...

CaMn0.875Ti0.125O3 as oxygen carrier for chemical-looping combustion with oxygen uncoupling (CLOU)—Experiments in a continuously operating fluidized-bed reactor system

KAUST Repository

Rydé n, Magnus; Lyngfelt, Anders; Mattisson, Tobias

2011-01-01

Particles of the perovskite material CaMn0.875Ti0.125O3 has been examined as oxygen carrier for chemical-looping with oxygen uncoupling, and for chemical-looping combustion of natural gas, by 70h of experiments in a circulating fluidized-bed reactor

Anion and cation diffusion in barium titanate and strontium titanate; Anionen- und Kationendiffusion in Barium- und Strontiumtitanat

Energy Technology Data Exchange (ETDEWEB)

Kessel, Markus Franz

2012-12-19

Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO{sub 3} single crystals has been studied by means of {sup 18}O{sub 2}/{sup 16}O{sub 2} isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material's bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial

Oxygen tracer diffusion and surface exchange kinetics in Ba0.5Sr0.5Co0.8Fe0.2O3-δ

NARCIS (Netherlands)

Berenov, A.; Atkinson, A.; Kilner, J.; Ananyev, M.; Eremin, V.; Porotnikova, N.; Farlenkov, A.; Kurumchin, E.; Bouwmeester, Henricus J.M.; Bucher, E.; Sitte, W.

2014-01-01

The oxygen tracer diffusion coefficient, Db⁎, and the oxygen tracer surface exchange coefficient, k, were measured in Ba0.5Sr0.5Co0.8Fe0.2O3 − δ (BSCF5582) over the temperature range of 310–800 °C and the oxygen partial pressure range of 1.3 × 10−3–0.21 bar. Several measurement techniques were used:

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

Science.gov (United States)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

Effect of Drying Temperature on the Chemical Properties and Diffusivity of belimbi (averrhoa belimbi)

Science.gov (United States)

Shahari, N.; Jamil, N.; Rasmani, K. A.; Nursabrina

2015-09-01

In recent years, many dried fruit products have been developed in response to a strong demand by the customer. This type of fruit has a different composition and hence different moisture diffusivity (D). During drying, Fick's Law of diffusion, which describes the movement of liquid water was used to calculate this diffusivity. However diffusivity has strong effects on the material drying characteristics and these must be determined. In this paper, Fick's Law of diffusion with different kinds of boundary conditions was solve using separation of variable (SOV). In order to get the value of D, results obtained using SOV will be compared with the results from the drying of belimbi at temperature of 40°C, 50°C and 60°C. Although the results show that variation in the values of diffusivity for different temperatures is relatively small, but the variation in the total time required for drying is significantly bigger: between 3-7 hours. Its shown that diffusivity is an important measurement and should be considered in the modeling of the drying process. The chemical properties of belimbi slices in terms of vitamin C, total ash and antioxidant activity with different air temperatures and pretreatment were also investigated. Higher drying temperatures gives less drying time, a lower vitamin C and antioxidant activity but a greater total of ash, whilst pre-treatment can increased vitamin C and antioxidant activity. The results show that pre-treatment and the drying temperature are important variables to improve mass and heat transfer, as well as the belimbi chemical properties.

Diffusivity, activity and solubility of oxygen in liquid lead and lead-bismuth eutectic alloy by electrochemical methods

International Nuclear Information System (INIS)

Ganesan, Rajesh; Gnanasekaran, T.; Srinivasa, Raman S.

2006-01-01

The diffusivity of oxygen in liquid lead and lead-bismuth eutectic (LBE) alloy was measured by a potentiostatic method and is given by log(D O Pb /cm 2 s -1 )=-2.554-2384/T(+/-0.070), 818-1061K, and log(D O LBE /cm 2 s -1 )=-0.813-3612/T(+/-0.091), 811-980K. The activity of oxygen in lead and LBE was determined by coulometric titration experiments. Using the measured data, the standard free energy of dissolution of oxygen in liquid lead and LBE was derived and is given byG O(Pb) xs =-121349+16.906T(+/-560)J(gatomO) -1 ,815-1090K,G O(LBE) xs = -127398+27.938T(+/-717)J(gatomO) -1 ,812-1012K.Using the above data, the Gibbs energy of formation of PbO(s) and equilibrium oxygen pressures measured over the oxygen-saturated LBE alloy, the solubility of oxygen in liquid lead and LBE were derived. The solubility of oxygen in liquid lead and LBE are given by log(S/at.%O)=-5100/T+4.32 (+/-0.04), 815-1090K and log(S/at.%O)=-4287/T+3.53 (+/-0.06), 812-1012K respectively.

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

Science.gov (United States)

Opila, Elizabeth J.

1994-01-01

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

Spatiotemporal chaos in the dynamics of buoyantly and diffusively unstable chemical fronts

Science.gov (United States)

Baroni, M. P. M. A.; Guéron, E.; De Wit, A.

2012-03-01

Nonlinear dynamics resulting from the interplay between diffusive and buoyancy-driven Rayleigh-Taylor (RT) instabilities of autocatalytic traveling fronts are analyzed numerically for various values of the relevant parameters. These are the Rayleigh numbers of the reactant A and autocatalytic product B solutions as well as the ratio D =DB/DA between the diffusion coefficients of the two key chemical species. The interplay between the coarsening dynamics characteristic of the RT instability and the constant short wavelength modulation of the diffusive instability can lead in some regimes to complex dynamics dominated by irregular succession of birth and death of fingers. By using spectral entropy measurements, we characterize the transition between order and spatial disorder in this system. The analysis of the power spectrum and autocorrelation function, moreover, identifies similarities between the various spatial patterns. The contribution of the diffusive instability to the complex dynamics is discussed.

Initial stages of oxidation of near-stoichiometric titanium carbide at low oxygen pressures

International Nuclear Information System (INIS)

Shabalin, I.L.; Vishnyakov, V.M.; Bull, D.J.; Keens, S.G.; Yamshchikov, L.F.; Shabalin, L.I.

2009-01-01

A novel approach to the oxidation mechanism of near-stoichiometric TiC is presented. It is confirmed by consideration of solid-state chemical kinetics model and electron microscopy observations in parallel. At low oxygen pressures and moderate temperatures the initial step of the process is connected with the dissolution of oxygen and subsequent decomposition of oxygen-oversaturated oxycarbide, which ultimately results in the nucleation of oxide phase, in particular anatase, belike stabilised by residual carbon. An anatase-rutile transformation is concurrent with deeper carbon burn-off in the oxide scale, which sinters at higher temperatures. This mechanism shifts the process to a gas diffusion regime, governed by the scale permeability, but determined by solid-state diffusion that is reflected in the kinetics, as further temperature increase is accompanied by a decrease of the oxidation rate, so in general the process is characterised by the negative value of apparent activation energy

Performance of calcium manganate as oxygen carrier in chemical looping combustion of biochar in a 10 kW pilot

International Nuclear Information System (INIS)

Schmitz, Matthias; Linderholm, Carl Johan

2016-01-01

Highlights: • A manganese-based perovskite material was used as oxygen carrier in chemical looping combustion. • The oxygen carrier’s performance was superior to materials previously tested in this reactor throughout the testing period. • Under stable conditions, oxygen demand was as low as 2.1% with a carbon capture efficiency of up to 98%. • No signs of agglomeration were detected. • Gaseous oxygen was released at all relevant fuel reactor temperatures. - Abstract: Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are carbon capture technologies which achieve gas separation by means of cycling oxidation and reduction of a solid oxygen carrier. In this study, the performance and CLOU properties of an oxygen carrier with perovskite structure, CaMn_0_._9Mg_0_._1O_3_−_δ_, were investigated in a 10 kW pilot. The fuel consisted of biochar with very low sulphur content. Around 37 h of operation with fuel were carried out in the 10 kW chemical looping combustor. Previous operational experience in this unit has been achieved using different natural minerals as oxygen carrier – mainly ilmenite and manganese ore. Parametric studies performed in this work included variation of fuel flow, solids circulation rate, temperature and fluidization gas in the fuel reactor. The oxygen carrier was exposed to a total 73 h of hot fluidization (T > 600 °C). No hard particle agglomerations were formed during the experiments. An oxygen demand as low as 2.1% could be reached under stable operating conditions, with a carbon capture efficiency of up to 98%. CLOU properties were observed at all fuel reactor temperatures, ensuring stable operation even without steam as gasification agent present in the fuel reactor. The results suggest that CaMn_0_._9Mg_0_._1O_3_−_δ is suitable for the use as oxygen carrier in chemical looping combustion of solid biochar and offers higher gas conversion than previously tested materials without CLOU

An Investigation into the Effects of Process Conditions on the Tribological Performance of Pack Carburized Titanium with Limited Oxygen Diffusion

Science.gov (United States)

Bailey, R.; Sun, Y.

2018-04-01

In the present study, a new pack carburization technique for titanium has been investigated. The aim of this treatment is to produce a titanium carbide/oxycarbide layer atop of an extended oxygen diffusion zone [α-Ti(O)]. The effects of treatment temperature and pack composition have been investigated in order to determine the optimal conditions required to grant the best tribological response. The resulting structural features were investigated with particular interest in the carbon and oxygen concentrations across the samples cross section. The optimization showed that a temperature of 925 °C with a pack composition of 1 part carbon to 1 part energizer produced surface capable of withstanding a contact pressure of ≈ 1.5 GPa for 1 h. The process resulted in TiC surface structure which offers enhanced hardness (2100 HV) and generates a low friction coefficient (μ ≈ 0.2) when in dry sliding contact with an alumina (Al2O3) ball. The process also produced an extended oxygen diffusion zone that helps to improve the load bearing capacity of the substrate.

Modeling of oxygen gas diffusion and consumption during the oxic transient in a disposal cell of radioactive waste

International Nuclear Information System (INIS)

De Windt, Laurent; Marsal, François; Corvisier, Jérôme; Pellegrini, Delphine

2014-01-01

Highlights: • This paper deals with the geochemistry of underground HLW disposals. • The oxic transient is a key issue in performance assessment (e.g. corrosion, redox). • A reactive transport model is explicitly coupled to gas diffusion and reactivity. • Application to in situ experiment (Tournemire laboratory) and HLW disposal cell. • Extent of the oxidizing/reducing front is investigated by sensitivity analysis. - Abstract: The oxic transient in geological radioactive waste disposals is a key issue for the performance of metallic components that may undergo high corrosion rates under such conditions. A previous study carried out in situ in the argillite formation of Tournemire (France) has suggested that oxic conditions could have lasted several years. In this study, a multiphase reactive transport model is performed with the code HYTEC to analyze the balance between the kinetics of pyrite oxidative dissolution, the kinetics of carbon steel corrosion and oxygen gas diffusion when carbon steel components are emplaced in the geological medium. Two cases were modeled: firstly, the observations made in situ have been reproduced, and the model established was then applied to a disposal cell for high-level waste (HLW) in an argillaceous formation, taking into account carbon steel components and excavated damaged zones (EDZ). In a closed system, modeling leads to a complete and fast consumption of oxygen in both cases. Modeling results are more consistent with the in situ test while considering residual voids between materials and/or a water unsaturated state allowing for oxygen gas diffusion (open conditions). Under similar open conditions and considering ventilation of the handling drifts, a redox contrast occurs between reducing conditions at the back of the disposal cell (with anoxic corrosion of steel and H 2 production) and oxidizing conditions at the front of the cell (with oxic corrosion of steel). The extent of the oxidizing/reducing front in the

Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

Directory of Open Access Journals (Sweden)

Alberta Silvestri

2017-01-01

Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

The relationship between alveolar oxygen tension and the single-breath carbon monoxide diffusing capacity.

Science.gov (United States)

Kanner, R E; Crapo, R O

1986-04-01

The effects of alveolar oxygen tension (PAO2) on the single-breath carbon monoxide diffusing capacity (DLCO) were quantified and a factor was derived to accommodate for differences in PAO2 over commonly encountered altitudes and/or varying concentrations of oxygen in the test gas mixture (FIO2) We performed duplicate measurements of DLCO in 7 normal subjects with 6 different oxygen fractions (0.176, 0.196, 0.211, 0.22, 0.25, and 0.27). The PAO2 for each test was measured as the PO2 in the alveolar gas sample bag. DLCO varied inversely with PAO2 and changed by 0.35% for each mmHg change in PAO2 (r = -0.62, p less than 0.001). At an FIO2 of 0.25, PAO2 varied between subjects and was highly correlated with each subject's residual volume to total lung capacity ratio (r = -0.84, p less than 0.001). We suggest that laboratories can adjust the measured DLCO when PAO2 is not congruent to 120 mmHg by the following formula: DLCO (corrected = DLCO (measured) x [1.0 + 0.0035 (PAO2 - 120)].

Mass transfer rate through liquid membranes: interfacial chemical reactions and diffusion as simultaneous permeability controlling factors

International Nuclear Information System (INIS)

Danesi, P.R.; Horwitz, E.P.; Vandegrift, G.F.; Chiarizia, R.

1981-01-01

Equations describing the permeability of a liquid membrane to metal cations have been derived taking into account aqueous diffusion, membrane diffusion, and interfacial chemical reactions as simultaneous permeability controlling factors. Diffusion and chemical reactions have been coupled by a simple model analogous to the one previously described by us to represent liquid-liquid extraction kinetics. The derived equations, which make use of experimentally determined interfacial reaction mechanisms, qualitatively fit unexplained literature data regarding Cu 2+ transfer through liquid membranes. Their use to predict and optimize membrane permeability in practical separation processes by setting the appropriate concentration of the membrane carrier [LIX 64 (General Mills), a commercial β-hydroxy-oxime] and the pH of the aqueous copper feed solution is briefly discussed. 4 figures

The Influence of Atomic Diffusion on Stellar Ages and Chemical Tagging

Energy Technology Data Exchange (ETDEWEB)

Dotter, Aaron; Conroy, Charlie; Cargile, Phillip [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138 (United States); Asplund, Martin, E-mail: aaron.dotter@gmail.com [Research School of Astronomy and Astrophysics, Australian National University, Canberra, ACT (Australia)

2017-05-10

In the era of large stellar spectroscopic surveys, there is an emphasis on deriving not only stellar abundances but also the ages for millions of stars. In the context of Galactic archeology, stellar ages provide a direct probe of the formation history of the Galaxy. We use the stellar evolution code MESA to compute models with atomic diffusion—with and without radiative acceleration—and extra mixing in the surface layers. The extra mixing consists of both density-dependent turbulent mixing and envelope overshoot mixing. Based on these models we argue that it is important to distinguish between initial, bulk abundances (parameters) and current, surface abundances (variables) in the analysis of individual stellar ages. In stars that maintain radiative regions on evolutionary timescales, atomic diffusion modifies the surface abundances. We show that when initial, bulk metallicity is equated with current, surface metallicity in isochrone age analysis, the resulting stellar ages can be systematically overestimated by up to 20%. The change of surface abundances with evolutionary phase also complicates chemical tagging, which is the concept that dispersed star clusters can be identified through unique, high-dimensional chemical signatures. Stars from the same cluster, but in different evolutionary phases, will show different surface abundances. We speculate that calibration of stellar models may allow us to estimate not only stellar ages but also initial abundances for individual stars. In the meantime, analyzing the chemical properties of stars in similar evolutionary phases is essential to minimize the effects of atomic diffusion in the context of chemical tagging.

Effects of chemical reaction on moving isothermal vertical plate with variable mass diffusion

Directory of Open Access Journals (Sweden)

Muthucumaraswamy R.

2003-01-01

Full Text Available An exact solution to the problem of flow past an impulsively started infinite vertical isothermal plate with variable mass diffusion is presented here, taking into account of the homogeneous chemical reaction of first-order. The dimensionless governing equations are solved by using the Laplace - transform technique. The velocity and skin-friction are studied for different parameters like chemical reaction parameter, Schmidt number and buoyancy ratio parameter. It is observed that the veloc­ity increases with decreasing chemical reaction parameter and increases with increasing buoyancy ratio parameter.

Diffusive oxygen shunting between vessels in the preglomerular renal vasculature: anatomic observations and computational modeling.

Science.gov (United States)

Gardiner, Bruce S; Thompson, Sarah L; Ngo, Jennifer P; Smith, David W; Abdelkader, Amany; Broughton, Brad R S; Bertram, John F; Evans, Roger G

2012-09-01

To understand how geometric factors affect arterial-to-venous (AV) oxygen shunting, a mathematical model of diffusive oxygen transport in the renal cortex was developed. Preglomerular vascular geometry was investigated using light microscopy (providing vein shape, AV separation, and capillary density near arteries) and published micro-computed tomography (CT) data (providing vessel size and AV separation; Nordsletten DA, Blackett S, Bentley MD, Ritman EL, Smith NP. IUPS Physiome Project. http://www.physiome.org.nz/publications/nordsletten_blackett_ritman_bentley_smith_2005/folder_contents). A "U-shaped" relationship was observed between the arterial radius and the distance between the arterial and venous lumens. Veins were found to partially wrap around the artery more consistently for larger rather than smaller arteries. Intrarenal arteries were surrounded by an area of fibrous tissue, lacking capillaries, the thickness of which increased from ∼5 μm for the smallest arteries (200-μm diameter). Capillary density was greater near smaller arteries than larger arteries. No capillaries were observed between wrapped AV vessel pairs. The computational model comprised a single AV pair in cross section. Geometric parameters critical in renal oxygen transport were altered according to variations observed by CT and light microscopy. Lumen separation and wrapping of the vein around the artery were found to be the critical geometric factors determining the amount of oxygen shunted between AV pairs. AV oxygen shunting increases both as lumen separation decreases and as the degree of wrapping increases. The model also predicts that capillaries not only deliver oxygen, but can also remove oxygen from the cortical parenchyma close to an AV pair. Thus the presence of oxygen sinks (capillaries or tubules) near arteries would reduce the effectiveness of AV oxygen shunting. Collectively, these data suggest that AV oxygen shunting would be favored in larger vessels common to the

Incorporating Embedded Microporous Layers into Topologically Equivalent Pore Network Models for Oxygen Diffusivity Calculations in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

International Nuclear Information System (INIS)

Fazeli, Mohammadreza; Hinebaugh, James; Bazylak, Aimy

2016-01-01

Highlights: • Pore network model for modeling PEMFC MPL-coated GDL effective diffusivity. • Bilayered GDL (substrate and MPL) is modeled with a hybrid network of block MPL elements combined with discrete substrate pores. • Diffusivities of MPL-coated GDLs agree with analytical solutions. - Abstract: In this work, a voxel-based methodology is introduced for the hybridization of a pore network with interspersed nano-porous material elements allowing pore network based oxygen diffusivity calculations in a 3D image of a polymer electrolyte membrane (PEM) fuel cell gas diffusion layer (GDL) with an embedded microporous layer (MPL). The composite GDL is modeled by combining a hybrid network of block MPL elements with prescribed bulk material properties and a topologically equivalent network of larger discrete pores and throats that are directly derived from the 3D image of the GDL substrate. This hybrid network was incorporated into a pore network model, and effective diffusivity predictions of GDL materials with MPL coatings were obtained. Stochastically generated numerical models of carbon paper substrates with and without MPLs were used, and the pore space was directly extracted from this realistic geometry as the input for the pore network model. The effective diffusion coefficient of MPL-coated GDL materials was predicted from 3D images in a pore network modeling environment without resolving the nano-scale structure of the MPL. This method is particularly useful due to the disparate length scales that are involved when attempting to capture pore-scale transport in the GDL. Validation was performed by comparing our predicted diffusivity values to analytical predictions, and excellent agreement was observed. Upon conducting a mesh sensitivity study, it was determined that an MPL element size of 7 μm provided sufficiently high resolution for accurately describing the MPL nano-structure.

Diffusion of 99-technetium in bentonite under aerobic and anaerobic conditions

International Nuclear Information System (INIS)

Vecernik, P.; Jedinakova-Krizova, V.; Vokal, A.

2006-01-01

Diffusion experiments were performed with 99 Tc and Re (a model of technetium) in the form of pertechnetate and perrhenate in bentonite from the Rokle locality (Czech Republic). The through diffusion method was used, and the apparent diffusion coefficients (D a ) were evaluated. The effects of the particle mesh-size, bulk densities, and aerobic or anaerobic conditions on the diffusion were studied in view of the fact that oxidizing or reducing conditions influence the chemical forms of technetium and rhenium. In the presence of oxygen, technetium and rhenium occur in oxidation state VII, as anions which are soluble and mobile in the environment, whereas in reducing conditions they occur in lower oxidation states, mainly as insoluble oxides or hydroxides. Aerobic experiments were carried out in common laboratory conditions, anaerobic experiments were performed under nitrogen

NEW CHEMICAL PROFILES FOR THE ASTEROSEISMOLOGY OF ZZ CETI STARS

International Nuclear Information System (INIS)

Althaus, L. G.; Corsico, A. H.; Romero, A. D.; Miller Bertolami, M. M.; Bischoff-Kim, A.; Renedo, I.; Garcia-Berro, E.

2010-01-01

We compute new chemical profiles for the core and envelope of white dwarfs appropriate for pulsational studies of ZZ Ceti stars. These profiles are extracted from the complete evolution of progenitor stars, evolved through the main sequence and the thermally pulsing asymptotic giant branch (AGB) stages, and from time-dependent element diffusion during white dwarf evolution. We discuss the importance of the initial-final mass relationship for the white dwarf carbon-oxygen composition. In particular, we find that the central oxygen abundance may be underestimated by about 15% if the white dwarf mass is assumed to be the hydrogen-free core mass before the first thermal pulse. We also discuss the importance for the chemical profiles expected in the outermost layers of ZZ Ceti stars of the computation of the thermally pulsing AGB phase and of the phase in which element diffusion is relevant. We find a strong dependence of the outer layer chemical stratification on the stellar mass. In particular, in the less massive models, the double-layered structure in the helium layer built up during the thermally pulsing AGB phase is not removed by diffusion by the time the ZZ Ceti stage is reached. Finally, we perform adiabatic pulsation calculations and discuss the implications of our new chemical profiles for the pulsational properties of ZZ Ceti stars. We find that the whole g-mode period spectrum and the mode-trapping properties of these pulsating white dwarfs as derived from our new chemical profiles are substantially different from those based on chemical profiles widely used in existing asteroseismological studies. Thus, we expect the asteroseismological models derived from our chemical profiles to be significantly different from those found thus far.

Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition

Energy Technology Data Exchange (ETDEWEB)

Salomé, Sónia; Rego, Rosa; Oliveira, M. Cristina, E-mail: mcris@utad.pt

2013-12-16

Silver-gas diffusion electrodes (Ag-GDE) were prepared by direct deposition of the catalyst onto a carbon paper support by electrodeposition. This deposition technique, under potentiostatic and galvanostatic mode, allows the production of well dispersed ultra-low Ag loading levels. The catalytic activity of the prepared materials towards the oxygen reduction reaction (ORR) was investigated in the alkaline solution and its tolerance to methanol was evaluated. Based on an Ag-ink prepared from the electrodeposit material and RDE experiments, it was concluded that the ORR occurs via a four-electron pathway on the Ag electrodeposit. The combination of reasonably high catalytic activity, efficiency, low price, facile and green synthesis makes the electrodeposited Ag-GDE attractive for the ORR in alkaline fuel cells. - Highlights: • A facile and simple way to successfully prepare catalyzed gas diffusion electrodes. • Ultra-low loadings of Ag-GDEs can be achieved. • Good tolerance to methanol and a high mass activity (3.14 mA{sub Ag} mg{sup −1}). • ORR occurs via a four-electron pathway.

Computational Analyses of Complex Flows with Chemical Reactions

Science.gov (United States)

Bae, Kang-Sik

The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic

Atomic resolution chemical bond analysis of oxygen in La2CuO4

Science.gov (United States)

Haruta, M.; Nagai, T.; Lugg, N. R.; Neish, M. J.; Nagao, M.; Kurashima, K.; Allen, L. J.; Mizoguchi, T.; Kimoto, K.

2013-08-01

The distorted CuO6 octahedron in La2CuO4 was studied using aberration-corrected scanning transmission electron microscopy at atomic resolution. The near-edge structure in the oxygen K-edge electron energy-loss spectrum was recorded as a function of the position of the electron probe. After background subtraction, the measured spectrum image was processed using a recently developed inversion process to remove the mixing of signals on the atomic columns due to elastic and thermal scattering. The spectra were then compared with first-principles band structure calculations based on the local-density approximation plus on-site Coulomb repulsion (LDA + U) approach. In this article, we describe in detail not only anisotropic chemical bonding of the oxygen 2p state with the Cu 3d state but also with the Cu 4p and La 5d/4f states. Furthermore, it was found that buckling of the CuO2 plane was also detectable at the atomic resolution oxygen K-edge. Lastly, it was found that the effects of core-hole in the O K-edge were strongly dependent on the nature of the local chemical bonding, in particular, whether it is ionic or covalent.

Pulsed chemical oxygen - iodine laser initiated by a transverse electric discharge

International Nuclear Information System (INIS)

Vagin, Nikolai P; Yuryshev, Nikolai N

2001-01-01

A pulsed chemical oxygen - iodine laser with a volume production of atomic iodine in a pulsed transverse electric discharge is studied. An increase in the partial oxygen pressure was shown to increase the pulse energy with retention of the pulse duration. At the same time, an increase in the iodide pressure and the discharge energy shortens the pulse duration. Pulses with a duration of 6.5 μs were obtained, which corresponds to a concentration of iodine atoms of 1.8 x 10 15 cm -3 . This concentration is close to the maximum concentration attained in studies of both cw and pulsed oxygen-iodine lasers. A specific energy output of 0.9 J litre -1 and a specific power of 75 kW litre -1 were obtained. The ways of increasing these parameters were indicated. It was found that SF 6 is an efficient buffer gas favouring improvements in the energy pulse parameters. (lasers)

Oxygen-vacancy defects on BaTiO3 (001) surface: a quantum chemical study

International Nuclear Information System (INIS)

Duque, Carlos; Stashans, Arvids

2003-01-01

A quantum-chemical study of technologically important BaTiO 3 crystal and oxygen-vacancy defects on its (001) surface is reported in the present work. The computations are made using a quantum-chemical method developed for periodic systems (crystals), which is based on the Hartree-Fock theory. The atomic rearrangement due to the surface creation is obtained for a pure BaTiO 3 by means of the periodic large unit cell (LUC) model and using an automated geometry optimisation procedure. The same technique is employed to study the electronic and structural properties of the material due to the presence of an O vacancy and F centre (two electrons trapped in an oxygen vacancy). The computations are carried out for both cubic and tetragonal lattices

Model of physico-chemical effect on flow accelerated corrosion in power plant

International Nuclear Information System (INIS)

Fujiwara, Kazutoshi; Domae, Masafumi; Yoneda, Kimitoshi; Inada, Fumio

2011-01-01

Highlights: → Model of chemical effect on FAC was developed. → Equation to evaluate the dissolved oxygen concentration for FAC suppression was derived. → The model explains the qualitatively the effect of parameters on FAC rate. → Diffusion of soluble species well reproduces the unique FAC behavior. - Abstract: Flow accelerated corrosion (FAC) is caused by the accelerated dissolution of protective oxide film under the condition of high flow rate and has been one of the most important subjects in fossil and nuclear power plants. The dominant factors of FAC are water chemistry, material, and fluid dynamics. Understanding of the thinning mechanism is very important to estimate the quantitative effects of the dominant factors on FAC. In this study, a novel model of chemical effect on FAC under the steady-state condition was developed in consideration of the diffusion of soluble iron and chromium species, dissolved hydrogen, and dissolved oxygen. The formula to evaluate the critical concentration of dissolved oxygen for FAC suppression was derived. The present model reproduced qualitatively the effect of major environmental parameters on FAC rate. The model could explain the following facts. (1) The FAC rate shows a peak around 413 K. (2) The FAC rate decreases with an increase in Cr content. (3) The FAC rate decreases with an increase in pH. (4) The FAC rate decreases with an increase in dissolved oxygen concentration. (5) The maximum of critical dissolved oxygen concentration is observed around 353 K. (6) The critical dissolved oxygen concentration decreases with an increase in pH. We conclude that the diffusion of soluble species from the saturated layer under the steady-state condition well reproduces the unique FAC behavior with variation of water chemistry parameters.

Oxygen transport in waterlogged soils, Part I. Approaches to modelling soil and crop response to oxygen deficiency

International Nuclear Information System (INIS)

Obando Moncayo, F.H.

2004-01-01

This lecture outlines in a simple way the mathematics of various cases of diffusion which have been widely used in modelling soil aeration. Simplifications of the general equation of diffusion (Fick's law) giving two possible forms of the problem: planar or one-dimensional diffusion and radial diffusion are given. Furthermore, the solution of diffusion equation is obtained by the analogy to the problem of electrical flow (Ohm's law). Taking into consideration the soil respiration process, the continuity equation which accounts for the law of conservation of mass is solved. The purpose of this paper has been to review the interrelation soil structure-air movement in waterlogged clay soils, and its consequences on plant growth and crop production. Thus, the mathematics of diffusion is presented, and then its application to specific cases of soil aeration such as diffusion in the soil profile, soil aggregates and roots is given. The following assumptions are taken into consideration. Gas flow in soils is basically diffusion-dependent. Gas-phase diffusion is the major mechanism for vertical or longitudinal transport (long distance transport); this means, with depth Z in the soil profile (macro diffusion). For horizontal transport (short distance transport or micro diffusion) which is assumed to be in X direction; in this case, the geometry of aggregates and the liquid phase are the major components of resistance for diffusion. Soil aggregates and roots are considered to be spherical and cylindrical in shape respectively. Soil oxygen consumption, Sr, is taken to be independent of the oxygen concentration and considered to proceed at the same rate until oxygen supply drops to critical levels. Thus, aeration problems are assumed to begin when at any time, in the root zone, the oxygen diffusion rate, ODR, becomes less than 30x10 -8 g.cm -2 .sec -1 , or the value of redox potential Eh is less than +525 mv

Controlled surface diffusion in plasma-enhanced chemical vapor deposition of GaN nanowires

International Nuclear Information System (INIS)

Hou, W C; Hong, Franklin Chau-Nan

2009-01-01

This study investigates the growth of GaN nanowires by controlling the surface diffusion of Ga species on sapphire in a plasma-enhanced chemical vapor deposition (CVD) system. Under nitrogen-rich growth conditions, Ga has a tendency to adsorb on the substrate surface diffusing to nanowires to contribute to their growth. The significance of surface diffusion on the growth of nanowires is dependent on the environment of the nanowire on the substrate surface as well as the gas phase species and compositions. Under nitrogen-rich growth conditions, the growth rate is strongly dependent on the surface diffusion of gallium, but the addition of 5% hydrogen in nitrogen plasma instantly diminishes the surface diffusion effect. Gallium desorbs easily from the surface by reaction with hydrogen. On the other hand, under gallium-rich growth conditions, nanowire growth is shown to be dominated by the gas phase deposition, with negligible contribution from surface diffusion. This is the first study reporting the inhibition of surface diffusion effects by hydrogen addition, which can be useful in tailoring the growth and characteristics of nanowires. Without any evidence of direct deposition on the nanowire surface, gallium and nitrogen are shown to dissolve into the catalyst for growing the nanowires at 900 deg. C.

Diffusion

International Nuclear Information System (INIS)

Kubaschewski, O.

1983-01-01

The diffusion rate values of titanium, its compounds and alloys are summarized and tabulated. The individual chemical diffusion coefficients and self-diffusion coefficients of certain isotopes are given. Experimental methods are listed which were used for the determination of diffusion coefficients. Some values have been taken over from other studies. Also given are graphs showing the temperature dependences of diffusion and changes in the diffusion coefficient with concentration changes

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

KAUST Repository

Wang, Zhandong

2017-11-28

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

KAUST Repository

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Hö inghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani

2017-01-01

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

Nonsuppressing normal thymus on chemical-shift MR imaging and anterior mediastinal lymphoma. Differentiation with diffusion-weighted MR imaging by using the apparent diffusion coefficient

International Nuclear Information System (INIS)

Priola, Adriano Massimiliano; Priola, Sandro Massimo; Gned, Dario; Veltri, Andrea; Giraudo, Maria Teresa

2018-01-01

To prospectively evaluate usefulness of the apparent diffusion coefficient (ADC) in differentiating anterior mediastinal lymphoma from nonsuppressing normal thymus on chemical-shift MR, and to look at the relationship between patient age and ADC. Seventy-three young subjects (25 men, 48 women; age range, 9-29 years), who underwent chemical-shift MR and diffusion-weighted MR were divided into a normal thymus group (group A, 40 subjects), and a lymphoma group (group B, 33 patients). For group A, all subjects had normal thymus with no suppression on opposed-phase chemical-shift MR. Two readers measured the signal intensity index (SII) and ADC. Differences in SII and ADC between groups were tested using t-test. ADC was correlated with age using Pearson correlation coefficient. Mean SII±standard deviation was 2.7±1.8% for group A and 2.2±2.4% for group B, with no significant difference between groups (P=.270). Mean ADC was 2.48±0.38 x 10 -3 mm 2 /s for group A and 1.24±0.23 x 10 -3 mm 2 /s for group B. A significant difference between groups was found (P<.001), with no overlap in range. Lastly, significant correlation was found between age and ADC (r=0.935, P<.001) in group A. ADC of diffusion-weighted MR is a noninvasive and accurate parameter for differentiating lymphoma from nonsuppressing thymus on chemical-shift MR in young subjects. (orig.)

Oxygen transport by oxygen potential gradient in dense ceramic oxide membranes

Energy Technology Data Exchange (ETDEWEB)

Maiya, P.S.; Balachandran, U.; Dusek, J.T.; Mieville, R.L. [Argonne National Lab., IL (United States). Energy Technology Div.; Kleefisch, M.S.; Udovich, C.A. [Amoco Exploration/Production, Naperville, IL (United States)

1996-05-01

Numerous studies have been conducted in recent years on the partial oxidation of methane to synthesis gas (syngas: CO + H{sub 2}) with air as the oxidant. In partial oxidation, a mixed-oxide ceramic membrane selectively transports oxygen from the air; this transport is driven by the oxygen potential gradient. Of the several ceramic materials the authors have tested, a mixed oxide based on the Sr-Fe-Co-O system has been found to be very attractive. Extensive oxygen permeability data have been obtained for this material in methane conversion experiments carried out in a reactor. The data have been analyzed by a transport equation based on the phenomenological theory of diffusion under oxygen potential gradients. Thermodynamic calculations were used to estimate the driving force for the transport of oxygen ions. The results show that the transport equation deduced from the literature describes the permeability data reasonably well and can be used to determine the diffusion coefficients and the associated activation energy of oxygen ions in the ceramic membrane material.

Real-time nonlinear feedback control of pattern formation in (bio)chemical reaction-diffusion processes: a model study.

Science.gov (United States)

Brandt-Pollmann, U; Lebiedz, D; Diehl, M; Sager, S; Schlöder, J

2005-09-01

Theoretical and experimental studies related to manipulation of pattern formation in self-organizing reaction-diffusion processes by appropriate control stimuli become increasingly important both in chemical engineering and cellular biochemistry. In a model study, we demonstrate here exemplarily the application of an efficient nonlinear model predictive control (NMPC) algorithm to real-time optimal feedback control of pattern formation in a bacterial chemotaxis system modeled by nonlinear partial differential equations. The corresponding drift-diffusion model type is representative for many (bio)chemical systems involving nonlinear reaction dynamics and nonlinear diffusion. We show how the computed optimal feedback control strategy exploits the system inherent physical property of wave propagation to achieve desired control aims. We discuss various applications of our approach to optimal control of spatiotemporal dynamics.

Detection and reduction of diffuse liquid and gas emissions in chemical and petrochemical industries; Ermittlung und Verminderung diffuser fluessiger und gasfoermiger Emissionen in der chemischen und petrochemischen Industrie

Energy Technology Data Exchange (ETDEWEB)

Koeppke, K.E. [Witten-Herdecke Univ. gGmbH, Witten (Germany). Inst. fuer Umwelttechnik und Management; Cuhls, C. [Halle-Wittenberg Univ., Halle (Germany). Inst. fuer Umwelttechnik

2002-09-01

In order to improve environmental protection, VOC emissions from diffuse sources are of growing importance. For the first time in Germany the present research report gives a detailed presentation of: constructive measures for the avoidance and reduction of diffuse emissions, adequate assembling procedures for equipments and installations, technical possibilities of leak detection and, different methods for the estimation of total emissions from chemical and petrochemical production plants. On the basis of own investigations and monitoring measures taken at various plants of chemical and petrochemical industries different measuring techniques for leak detection as well as methods for the estimation of total emissions from diffuse sources are analysed and their limits are described. (orig.)

On the influence of hydronium and hydroxide ion diffusion on the hydrogen and oxygen evolution reactions in aqueous media

DEFF Research Database (Denmark)

Wiberg, Gustav Karl Henrik; Arenz, Matthias

2015-01-01

We present a study concerning the influence of the diffusion of H+ and OH- ions on the hydrogen and oxygen evolution reactions (HER and OER) in aqueous electrolyte solutions. Using a rotating disk electrode (RDE), it is shown that at certain conditions the observed current, i.e., the reaction rate...

Introducing Barium in Transition Metal Oxide Frameworks: Impact upon Superconductivity, Magnetism, Multiferroism and Oxygen Diffusion and Storage.

Science.gov (United States)

Raveau, Bernard

2017-06-01

The role of barium in the structural chemistry of some transition metal oxides of the series "Cu, Mn, Fe,Co" is reviewed, based on its size effect and its particular chemical bonding. Its impact upon various properties, superconductivity, magnetism, multiferroism, oxygen storage is emphasized. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The evaluation of secondary system oxygen-scavenging chemicals using a water-circulating rig

Energy Technology Data Exchange (ETDEWEB)

Collins, M.W. [Nuclear Dept., HMS Sultan (United Kingdom)

2002-07-01

To assess the efficiency, mode of action and possible by-products of chemical dosing agents, e.g. oxygen scavengers, a circulating water rig was constructed. The rig uses a demineralized water supply as a source of make-up water to fill a recirculating loop of approx. 10 litres volume. The rig pipework is made of polythene with standard off-the shelf pipe fittings and connectors. The following parameters can be measured within the rig: pH and conductivity measured by in-line monitor, dissolved oxygen level, temperature. The system has already been used for some preliminary testing. The following oxygen scavengers have been used for tests: ascorbic acid (vitamin C), N,N-diethyl-hydroxylamine (DEHA), Hydroquinone, hydrazine hydrate and anhydrous sodium sulfite. (authors)

The evaluation of secondary system oxygen-scavenging chemicals using a water-circulating rig

International Nuclear Information System (INIS)

Collins, M.W.

2002-01-01

To assess the efficiency, mode of action and possible by-products of chemical dosing agents, e.g. oxygen scavengers, a circulating water rig was constructed. The rig uses a demineralized water supply as a source of make-up water to fill a recirculating loop of approx. 10 litres volume. The rig pipework is made of polythene with standard off-the shelf pipe fittings and connectors. The following parameters can be measured within the rig: pH and conductivity measured by in-line monitor, dissolved oxygen level, temperature. The system has already been used for some preliminary testing. The following oxygen scavengers have been used for tests: ascorbic acid (vitamin C), N,N-diethyl-hydroxylamine (DEHA), Hydroquinone, hydrazine hydrate and anhydrous sodium sulfite. (authors)

Effect of vapor-phase oxygen on chemical vapor deposition growth of graphene

Science.gov (United States)

Terasawa, Tomo-o.; Saiki, Koichiro

2015-03-01

To obtain a large-area single-crystal graphene, chemical vapor deposition (CVD) growth on Cu is considered the most promising. Recently, the surface oxygen on Cu has been found to suppress the nucleation of graphene. However, the effect of oxygen in the vapor phase was not elucidated sufficiently. Here, we investigate the effect of O2 partial pressure (PO2) on the CVD growth of graphene using radiation-mode optical microscopy. The nucleation density of graphene decreases monotonically with PO2, while its growth rate reaches a maximum at a certain pressure. Our results indicate that PO2 is an important parameter to optimize in the CVD growth of graphene.

Morphological, Chemical Surface, and Diffusive Transport Characterizations of a Nanoporous Alumina Membrane

Directory of Open Access Journals (Sweden)

María I. Vázquez

2015-12-01

Full Text Available Synthesis of a nanoporous alumina membrane (NPAM by the two-step anodization method and its morphological and chemical surface characterization by analyzing Scanning Electron Microscopy (SEM micrographs and X-Ray Photoelectron Spectroscopy (XPS spectra is reported. Influence of electrical and diffusive effects on the NaCl transport across the membrane nanopores is determined from salt diffusion measurements performed with a wide range of NaCl concentrations, which allows the estimation of characteristic electrochemical membrane parameters such as the NaCl diffusion coefficient and the concentration of fixed charges in the membrane, by using an appropriated model and the membrane geometrical parameters (porosity and pore length. These results indicate a reduction of ~70% in the value of the NaCl diffusion coefficient through the membrane pores with respect to solution. The transport number of ions in the membrane pores (Na+ and Cl−, respectively were determined from concentration potential measurements, and the effect of concentration-polarization at the membrane surfaces was also considered by comparing concentration potential values obtained with stirred solutions (550 rpm and without stirring. From both kinds of results, a value higher than 0.05 M NaCl for the feed solution seems to be necessary to neglect the contribution of electrical interactions in the diffusive transport.

Impact of thermal conductivity models on the coupling of heat transport, oxygen diffusion, and deformation in (U, Pu)O nuclear fuel elements

Science.gov (United States)

Mihaila, Bogdan; Stan, Marius; Crapps, Justin; Yun, Di

2013-02-01

We study the coupled thermal transport, oxygen diffusion, and thermal expansion in a generic nuclear fuel rod consisting of a (U) fuel pellet separated by a helium gap from zircaloy cladding. Steady-state and time-dependent finite-element simulations with a variety of initial- and boundary-value conditions are used to study the effect of the Pu content, y, and deviation from stoichiometry, x, on the temperature and deformation profiles in this fuel element. We find that the equilibrium radial temperature and deformation profiles are most sensitive to x at small values of y. For larger values of y, the effects of oxygen and Pu content are equally important. Following a change in the heat-generation rate, the centerline temperature, the radial deformation of the fuel pellet, and the centerline deviation from stoichiometry track each other closely in (U,Pu)O, as the characteristic time scales of the heat transport and oxygen diffusion are similar. This result is different from the situation observed in the case of UO fuels.

Quantitation of chemical exchange rates using pulsed-field-gradient diffusion measurements

International Nuclear Information System (INIS)

Andrec, Michael; Prestegard, James H.

1997-01-01

A new approach to the quantitation of chemical exchange rates is presented, and its utility is illustrated with application to the exchange of protein amide protons with bulk water. The approach consists of a selective-inversion exchange HMQC experiment in which a short spin echo diffusion filter has been inserted into the exchange period. In this way, the kinetics of exchange are encoded directly in an apparent diffusion coefficient which is a function of the position of the diffusion filter in the pulse sequence. A detailed theoretical analysis of this experiment indicates that, in addition to the measurement of simple exchange rates, the experiment is capable of measuring the effect of mediated exchange, e.g. the transfer of magnetization from bulk water to an amide site mediated by an internal bound water molecule or a labile protein side-chain proton in fast exchange with bulk water. Experimental results for rapid water/amide exchange in acyl carrier protein are shown to be quantitatively consistent with the exchange rates measured using a selective-inversion exchange experiment

Oxygen effect and intracellular oxygen content (adaptation hypothesis)

Energy Technology Data Exchange (ETDEWEB)

Yarmonenko, S P; Ehpshtejn, I M [Akademiya Meditsinskikh Nauk SSSR, Moscow. Onkologicheskij Tsentr

1977-01-01

Experimental data indicating that a radiomodifying action of hypoxia is dependent on the ''prehistory'' of the irradiated object are considered. This dependence manifests itself in a decreased protective action of acute hypoxia on the hypoxia-adapted objects. To explain this a hypothesis is proposed connecting a degree of cell radiosensitivity modification, determined by the oxygen effect, with the intracellular oxygen content. The latter, in accord with current ideas, is regulated by variations in the diffusion resistance to oxygen shown by the cytoplasmic membranes depending on the energy level of the cell and the degree of its oxygenation.

Oxygen effect and intracellular oxygen content (adaptation hypothesis)

International Nuclear Information System (INIS)

Yarmonenko, S.P.; Ehpshtejn, I.M.

1977-01-01

Experimental data indicating that a radiomodifying action of hypoxia is dependent on the ''prehistory'' of the irradiated object are considered. This dependence manifests itself in a decreased protective action of acute hypoxia on the hypoxia-adapted objects. To explain this a hypothesis is proposed connecting a degree of cell radiosensitivity modification, determined by the oxygen effect, with the intracellular oxygen content. The latter, in accord with current ideas, is regulated by variations in the diffusion resistance to oxygen shown by the cytoplasmic membranes depending on the energy level of the cell and the degree of its oxygenation

Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material

Directory of Open Access Journals (Sweden)

Kata Hajdu

2017-12-01

Full Text Available Photosynthetic reaction center proteins (RCs are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs. Carboxyl—and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of 1O2 either by physical (resonance energy transfer or by chemical (oxidation reaction and their efficiency showed dependence on the diffusion distance of 1O2.

Generation of atomic iodine via fluorine for chemical oxygen-iodine laser

Czech Academy of Sciences Publication Activity Database

Jirásek, Vít; Špalek, Otomar; Čenský, Miroslav; Picková, Irena; Kodymová, Jarmila; Jakubec, Ivo

2007-01-01

Roč. 334, - (2007), s. 167-174 ISSN 0301-0104 R&D Projects: GA ČR GA202/05/0359 Grant - others:USAF European Office for Research and Development(XE) FA 8655-05-M-4027 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z40320502 Keywords : atomic iodine * atomic fluorine * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.805, year: 2007

Oxygen diffusion pathways in a cofactor-independent dioxygenase

Science.gov (United States)

Di Russo, Natali V.; Condurso, Heather L.; Li, Kunhua; Bruner, Steven D.; Roitberg, Adrian E.

2015-01-01

Molecular oxygen plays an important role in a wide variety of enzymatic reactions. Through recent research efforts combining computational and experimental methods a new view of O2 diffusion is emerging, where specific channels guide O2 to the active site. The focus of this work is DpgC, a cofactor-independent oxygenase. Molecular dynamics simulations, together with mutagenesis experiments and xenon-binding data, reveal that O2 reaches the active site of this enzyme using three main pathways and four different access points. These pathways connect a series of dynamic hydrophobic pockets, concentrating O2 at a specific face of the enzyme substrate. Extensive molecular dynamics simulations provide information about which pathways are more frequently used. This data is consistent with the results of kinetic measurements on mutants and is difficult to obtain using computational cavity-location methods. Taken together, our results reveal that although DpgC is rare in its ability of activating O2 in the absence of cofactors or metals, the way O2 reaches the active site is similar to that reported for other O2-using proteins: multiple access channels are available, and the architecture of the pathway network can provide regio- and stereoselectivity. Our results point to the existence of common themes in O2 access that are conserved among very different types of proteins. PMID:26508997

Real-Time Molecular Monitoring of Chemical Environment in ObligateAnaerobes during Oxygen Adaptive Response

Energy Technology Data Exchange (ETDEWEB)

Holman, Hoi-Ying N.; Wozei, Eleanor; Lin, Zhang; Comolli, Luis R.; Ball, David. A.; Borglin, Sharon; Fields, Matthew W.; Hazen, Terry C.; Downing, Kenneth H.

2009-02-25

Determining the transient chemical properties of the intracellular environment canelucidate the paths through which a biological system adapts to changes in its environment, for example, the mechanisms which enable some obligate anaerobic bacteria to survive a sudden exposure to oxygen. Here we used high-resolution Fourier Transform Infrared (FTIR) spectromicroscopy to continuously follow cellular chemistry within living obligate anaerobes by monitoring hydrogen bonding in their cellular water. We observed a sequence of wellorchestrated molecular events that correspond to changes in cellular processes in those cells that survive, but only accumulation of radicals in those that do not. We thereby can interpret the adaptive response in terms of transient intracellular chemistry and link it to oxygen stress and survival. This ability to monitor chemical changes at the molecular level can yield important insights into a wide range of adaptive responses.

Determination of oxygen content and carbonate impurity in YBa2Cu3O7-x by diffuse reflectance infrared spectroscopy

International Nuclear Information System (INIS)

Merzbacher, C.I.; Bonner, B.P.

1991-01-01

Samples of YBa 2 Cu 3 O 7-x with x ranging from ∼0 to 0.65 have been analyzed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in the midinfrared region (400--6000 cm -1 ). Spectral line shapes vary gradually as a function of oxygen stoichiometry, and the reflectance at 400 and 1000 cm -1 decreases linearly with decreasing oxygen content. Spectra of samples that were incompletely synthesized or exposed to a 4% CO 2 atmosphere at 650 degree C clearly indicated the presence of carbonate. DRIFTS is therefore a quick, nondestructive method for determining oxygen content in YBa 2 Cu 3 O 7-x powders, and for detecting carbonate species due to synthesis error or reaction with CO 2 -bearing atmosphere

The Pathway for Oxygen: Tutorial Modelling on Oxygen Transport from Air to Mitochondrion: The Pathway for Oxygen.

Science.gov (United States)

Bassingthwaighte, James B; Raymond, Gary M; Dash, Ranjan K; Beard, Daniel A; Nolan, Margaret

2016-01-01

The 'Pathway for Oxygen' is captured in a set of models describing quantitative relationships between fluxes and driving forces for the flux of oxygen from the external air source to the mitochondrial sink at cytochrome oxidase. The intervening processes involve convection, membrane permeation, diffusion of free and heme-bound O2 and enzymatic reactions. While this system's basic elements are simple: ventilation, alveolar gas exchange with blood, circulation of the blood, perfusion of an organ, uptake by tissue, and consumption by chemical reaction, integration of these pieces quickly becomes complex. This complexity led us to construct a tutorial on the ideas and principles; these first PathwayO2 models are simple but quantitative and cover: (1) a 'one-alveolus lung' with airway resistance, lung volume compliance, (2) bidirectional transport of solute gasses like O2 and CO2, (3) gas exchange between alveolar air and lung capillary blood, (4) gas solubility in blood, and circulation of blood through the capillary syncytium and back to the lung, and (5) blood-tissue gas exchange in capillaries. These open-source models are at Physiome.org and provide background for the many respiratory models there.

Calcium and chemical looping technology for power generation and carbon dioxide (CO2) capture solid oxygen- and CO2-carriers

CERN Document Server

Fennell, Paul

2015-01-01

Calcium and Chemical Looping Technology for Power Generation and Carbon Dioxide (CO2) Capture reviews the fundamental principles, systems, oxygen carriers, and carbon dioxide carriers relevant to chemical looping and combustion. Chapters review the market development, economics, and deployment of these systems, also providing detailed information on the variety of materials and processes that will help to shape the future of CO2 capture ready power plants. Reviews the fundamental principles, systems, oxygen carriers, and carbon dioxide carriers relevant to calcium and chemical loopingProvi

Manual or automated measuring of antipsychotics' chemical oxygen demand.

Science.gov (United States)

Pereira, Sarah A P; Costa, Susana P F; Cunha, Edite; Passos, Marieta L C; Araújo, André R S T; Saraiva, M Lúcia M F S

2018-05-15

Antipsychotic (AP) drugs are becoming accumulated in terrestrial and aqueous resources due to their actual consumption. Thus, the search of methods for assessing the contamination load of these drugs is mandatory. The COD is a key parameter used for monitoring water quality upon the assessment of the effect of polluting agents on the oxygen level. Thus, the present work aims to assess the chemical oxygen demand (COD) levels of several typical and atypical antipsychotic drugs in order to obtain structure-activity relationships. It was implemented the titrimetric method with potassium dichromate as oxidant and a digestion step of 2h, followed by the measurement of remained unreduced dichromate by titration. After that, an automated sequential injection analysis (SIA) method was, also, used aiming to overcome some drawbacks of the titrimetric method. The results obtained showed a relationship between the chemical structures of antipsychotic drugs and their COD values, where the presence of aromatic rings and oxidable groups give higher COD values. It was obtained a good compliance between the results of the reference batch procedure and the SIA system, and the APs were clustered in two groups, with the values ratio between the methodologies, of 2 or 4, in the case of lower or higher COD values, respectively. The SIA methodology is capable of operating as a screening method, in any stage of a synthetic process, being also more environmentally friendly, and cost-effective. Besides, the studies presented open promising perspectives for the improvement of the effectiveness of pharmaceutical removal from the waste effluents, by assessing COD values. Copyright © 2018 Elsevier Inc. All rights reserved.

Creep effects in diffusion bonding of oxygen-free copper

CERN Document Server

Moilanen, Antti

Diffusion is the transport of atoms or particles through the surrounding material. Various microstructural changes in metals are based on the diffusion phenomena. In solid metals the diffusion is closely related to crystallographic defects. In single-component metals the dominant mechanism of diffusion is the vacancy mechanism. Diffusion bonding is a direct technological application of diffusion. It is an advanced solidstate joining process in which the surfaces of two components are brought to contact with each other and heated under a pressing load in a controlled environment. During the process, the contact surfaces are bonded by atomic diffusion across the interface and as a result, one solid piece is formed. The condition of high temperature and low applied stress combined with relatively long process duration enables the creep effects to take place in bonded metals. Furthermore, creep causes unwanted permanent deformations in the bonded components. Some authors suggest that there could be a threshold fo...

Oxygen Transport Membrane Reactors for Oxy-Fuel Combustion and Carbon Capture Purposes

Science.gov (United States)

Falkenstein-Smith, Ryan L.

This thesis investigates oxygen transport membrane reactors (OTMs) for the application of oxy-fuel combustion. This is done by evaluating the material properties and oxygen permeability of different OTM compositions subjected to a variety of operating conditions. The scope of this work consists of three components: (1) evaluate the oxygen permeation capabilities of perovskite-type materials for the application of oxy-fuel combustion; (2) determine the effects of dual-phase membrane compositions on the oxygen permeation performance and membrane characteristics; and (3) develop a new method for estimating the oxygen permeation performance of OTMs utilized for the application of oxy-fuel combustion. SrSc0.1Co0.9O3-delta (SSC) is selected as the primary perovskite-type material used in this research due to its reported high ionic and electronic conductive properties and chemical stability. SSC's oxygen ion diffusivity is investigated using a conductivity relaxation technique and thermogravimetric analysis. Material properties such as chemical structure, morphology, and ionic and electronic conductivity are examined by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), and conductivity testing using a four-probe method, respectively. Oxygen permeation tests study the oxygen permeability OTMs under modified membrane temperatures, sweeping gas flow rates, sweeping gas compositions, membrane configurations, and membrane compositions. When utilizing a pure CO2 sweeping gas, the membrane composition was modified with the addition of Sm0.2Ce0.8O1.9-delta (SDC) at varying wt.% to improve the membranes mechanical stability. A newly developed method to evaluate the oxygen permeation performance of OTMs is also presented by fitting OTM's oxygen permeability to the methane fraction in the sweeping gas composition. The fitted data is used to estimate the overall performance and size of OTMs utilized for the application of oxy-fuel combustion. The findings from this

Evolution of factors affecting placental oxygen transfer

DEFF Research Database (Denmark)

Carter, A M

2009-01-01

A review is given of the factors determining placental oxygen transfer and the oxygen supply to the fetus. In the case of continuous variables, such as the rate of placental blood flow, it is not possible to trace evolutionary trends. Discontinuous variables, for which we can define character sta......, where fetal and adult haemoglobin are not different, developmental regulation of 2, 3-diphosphoglycerate ensures the high oxygen affinity of fetal blood. Oxygen diffusing capacity is dependent on diffusion distance, which may vary with the type of interhaemal barrier. It has been shown...

Comparative evaluation of diffusion hypoxia and psychomotor skills with or without postsedation oxygenation following administration of nitrous oxide in children undergoing dental procedures: A clinical study.

Science.gov (United States)

Khinda, Vineet Inder Singh; Bhuria, Parvesh; Khinda, Paramjit; Kallar, Shiminder; Brar, Gurlal Singh

2016-01-01

Diffusion hypoxia is the most serious potential complication associated with nitrous oxide. It occurs during the recovery period. Hence, administration of 100% oxygen is mandatory as suggested by many authors. The aim of this study is to evaluate the occurrence/nonoccurrence of diffusion hypoxia in two groups of patients undergoing routine dental treatment under nitrous oxide sedation when one group is subjected to 7 min of postsedation oxygenation and the second group of the patients is made to breathe room air for the similar period. A total of sixty patients within the age group of 7-10 years requiring invasive dental procedures were randomly divided into two groups of 30 each using chit method. In the control group, patients were administered 100% oxygen postsedation, whereas, in the study group, patients were made to breathe room air postsedation. Various parameters (pulse rate, respiratory rate, blood pressure, and oxygen saturation [SpO2]) were recorded pre- and post-operatively. Data were collected and then sent for statistical analysis. The mean postoperative SpO2 at measurement times 1, 3, 5, and 7 min in both the groups was higher than the mean preoperative SpO2. This increase was statistically significant. No significant difference was found between the Trieger test scores. This study proves that clinical occurrence of diffusion hypoxia is not possible while following the routine procedure of nitrous oxide sedation.

Vanadium diffusion coating on HT-9 cladding for mitigating the fuel cladding chemical interactions

Science.gov (United States)

Lo, Wei-Yang; Yang, Yong

2014-08-01

Fuel cladding chemical interaction (FCCI) has been identified as one of the crucial issues for developing Ferritic/Martensitic (F/M) stainless steel claddings for metallic fuels in a fast reactor. The anticipated elevated temperature and high neutron flux can significantly aggravate the FCCI, in terms of formation of inter-diffusion and lower melting point eutectic phases. To mitigate the FCCI, vanadium carbide coating as a diffusion barrier was deposited on the HT-9 substrate using a pack cementation diffusion coating (PCDC) method, and the processing temperature was optimized down to 730 °C. A solid metallurgical bonding between the coating layer and substrate was achieved, and the coating is free from through depth cracks. The microstructural characterizations using SEM and TEM show a nanostructured grain structure. EDS/WDS and XRD analysis confirm the phase of coating layer as V2C. Diffusion couple tests at 660 °C for 100 h demonstrate that V2C layer with a thickness of less than 5 μm can effectively eliminate the inter-diffusion between the lanthanide cerium and HT-9 steel.

Vanadium diffusion coating on HT-9 cladding for mitigating the fuel cladding chemical interactions

Energy Technology Data Exchange (ETDEWEB)

Lo, Wei-Yang; Yang, Yong, E-mail: yongyang@ufl.edu

2014-08-01

Fuel cladding chemical interaction (FCCI) has been identified as one of the crucial issues for developing Ferritic/Martensitic (F/M) stainless steel claddings for metallic fuels in a fast reactor. The anticipated elevated temperature and high neutron flux can significantly aggravate the FCCI, in terms of formation of inter-diffusion and lower melting point eutectic phases. To mitigate the FCCI, vanadium carbide coating as a diffusion barrier was deposited on the HT-9 substrate using a pack cementation diffusion coating (PCDC) method, and the processing temperature was optimized down to 730 °C. A solid metallurgical bonding between the coating layer and substrate was achieved, and the coating is free from through depth cracks. The microstructural characterizations using SEM and TEM show a nanostructured grain structure. EDS/WDS and XRD analysis confirm the phase of coating layer as V{sub 2}C. Diffusion couple tests at 660 °C for 100 h demonstrate that V{sub 2}C layer with a thickness of less than 5 μm can effectively eliminate the inter-diffusion between the lanthanide cerium and HT-9 steel.

Use and abuse of diffusion

International Nuclear Information System (INIS)

Kwiotek, A.; Grzywna, Z.J.

2005-01-01

Diffusion in a bounded region (or diffusive mass transport) can be seen from at least three platforms: - chemistry of he Fick's equation; - chemical engineering. To pose a particular problem we have to provide some additional conditions (initial conditions, boundary conditions and further). As we understood it in all cases diffusion is considered in an open region (in other words in one phase). Chemical engineering however brings an idea of 'diffusion' between phases. We claim that there isn't diffusion between phases. One can only consider mass transport between phases. Mass transport (or transfer in chemical engineering jargon) from one phase to another composes of: diffusion in first phase partition at an interface diffusion in second phase. (author)

Miniaturized and green method for determination of chemical oxygen demand using UV-induced oxidation with hydrogen peroxide and single drop microextraction

International Nuclear Information System (INIS)

Akhoundzadeh, Jeyran; Chamsaz, Mahmoud; Costas, Marta; Lavilla, Isela; Bendicho, Carlos

2013-01-01

We report on a green method for the determination of low levels of chemical oxygen demand. It is based on the combination of (a) UV-induced oxidation with hydrogen peroxide, (b) headspace single-drop microextraction with in-drop precipitation, and (c) micro-turbidimetry. The generation of CO 2 after photolytic oxidation followed by its sequestration onto a microdrop of barium hydroxide gives rise to a precipitate of barium carbonate which is quantified by turbidimetry. UV-light induced oxidation was studied in the absence and presence of H 2 O 2 , ultrasound, and ferrous ion. Determinations of chemical oxygen demand were performed using potassium hydrogen phthalate as a model compound. The optimized method gives a calibration curve that is linear between 3.4 and 20 mg L −1 oxygen. The detection limit was 1.2 mg L −1 of oxygen, and the repeatability (as relative standard deviation) was around 5 %. The method was successfully applied to the determination of chemical oxygen demand in different natural waters and a synthetic wastewater. (author)

Mechanism of dark decomposition of iodine donor in the active medium of a pulsed chemical oxygen - iodine laser

International Nuclear Information System (INIS)

Andreeva, Tamara L; Kuznetsova, S V; Maslov, A I; Sorokin, Vadim N

2002-01-01

A scheme is proposed that describes the dark decomposition of iodide - the donor of iodine - and the relaxation of singlet oxygen in the chlorine-containing active medium of a pulsed chemical oxygen - iodine laser (COIL). For typical compositions of the active media of pulsed COILs utilising CH 3 I molecules as iodine donors, a branching chain reaction of the CH 3 I decomposition accompanied by the efficient dissipation of singlet oxygen is shown to develop even at the stage of filling the active volume. In the active media with CF 3 I as the donor, a similar chain reaction is retarded due to the decay of CF 3 radicals upon recombination with oxygen. The validity of this mechanism is confirmed by a rather good agreement between the results of calculations and the available experimental data. The chain decomposition of alkyliodides accompanied by an avalanche production of iodine atoms represents a new way of efficient chemical production of iodine for a COIL. (active media)

Adsorption of oxygen on low-index surfaces of the TiAl{sub 3} alloy

Energy Technology Data Exchange (ETDEWEB)

Latyshev, A. M.; Bakulin, A. V.; Kulkova, S. E., E-mail: kulkova@ms.tsc.ru [National Research Tomsk State University (Russian Federation); Hu, Q. M.; Yang, R. [Chinese Academy of Sciences, Shenyang National Laboratory for Materials Science, Institute of Metal Research (China)

2016-12-15

Method of the projector augmented waves in the plane-wave basis within the generalized-gradient approximation for the exchange-correlation functional has been used to study oxygen adsorption on (001), (100), and (110) low-index surfaces of the TiAl{sub 3} alloy. It has been established that the sites that are most energetically preferred for the adsorption of oxygen are hollow (H) positions on the (001) surface and bridge (B) positions on the (110) and (100) surfaces. Structural and electronic factors that define their energy preference have been discussed. Changes in the atomic and electronic structure of subsurface layers that occur as the oxygen concentration increases to three monolayers have been analyzed. It has been shown that the formation of chemical bonds of oxygen with both components of the alloy leads to the appearance of states that are split-off from the bottoms of their valence bands, which is accompanied by the formation of a forbidden gap at the Fermi level and by a weakening of the Ti–Al metallic bonds in the alloy. On the Al-terminated (001) and (110) surfaces, the oxidation of aluminum dominates over that of titanium. On the whole, the binding energy of oxygen on the low-index surfaces with a mixed termination is higher than that at the aluminum-terminated surface. The calculation of the diffusion of oxygen in the TiAl{sub 3} alloy has shown that the lowest barriers correspond to the diffusion between tetrahedral positions in the (001) plane; the diffusion of oxygen in the [001] direction occurs through octahedral and tetrahedral positions. An increase in the concentration of aluminum in the alloy favors a reduction in the height of the energy barriers as compared to the corresponding barriers in the γ-TiAl alloy.

Understanding Oxygen Vacancy Formation, Interaction, Transport, and Strain in SOFC Components via Combined Thermodynamics and First Principles Calculations

Science.gov (United States)

Das, Tridip

Understanding of the vacancy formation, interaction, increasing its concentration and diffusion, and controlling its chemical strain will advance the design of mixed ionic and electronic conductor (MIEC) materials via element doping and strain engineering. This is especially central to improve the performance of the solid oxide fuel cell (SOFC), an energy conversion device for sustainable future. The oxygen vacancy concentration grows exponentially with the temperature at dilute vacancy concentration but not at higher concentration, or even decreases due to oxygen vacancy interaction and vacancy ordered phase change. This limits the ionic conductivity. Using density functional theory (DFT), we provided fundamental understanding on how oxygen vacancy interaction originates in one of the typical MIEC, La1-xSrxFeO3-delta (LSF). The vacancy interaction is determined by the interplay of the charge state of multi-valence ion (Fe), aliovalent doping (La/Sr ratio), the crystal structure, and the oxygen vacancy concentration and/or nonstoichiometry (delta). It was found excess electrons left due to the formation of a neutral oxygen vacancy get distributed to Fe directly connected to the vacancy or to the second nearest neighboring Fe, based on crystal field splitting of Fe 3d orbital in different Fe-O polyhedral coordination. The progressively larger polaron size and anisotropic shape changes with increasing Sr-content resulted in increasing oxygen vacancy interactions, as indicated by an increase in the oxygen vacancy formation energy above a critical delta threshold. This was consistent with experimental results showing that Sr-rich LSF and highly oxygen deficient compositions are prone to oxygen-vacancy-ordering-induced phase transformations, while Sr-poor and oxygen-rich LSF compositions are not. Since oxygen vacancy induced phase transformations, cause a decrease in the mobile oxygen vacancy site fraction (X), both delta and X were predicted as a function of

Chemical compatibility study of lithium titanate with Indian reduced activation ferritic martensitic steel

International Nuclear Information System (INIS)

Sonak, Sagar; Jain, Uttam; Haldar, Rumu; Kumar, Sanjay

2015-01-01

Highlights: • Chemical compatibility between Li_2TiO_3 and Indian RAFM steel has been studied at ITER operating temperature. • The lithium titanate chemically reacted with ferritic martensitic steel to form a brittle and non-adherent oxide layer. • The layer grew in a parabolic manner as a function of heating time. • Diffusion of oxygen (from Li_2TiO_3) appears to be controlling the oxide layer. - Abstract: Chemical compatibility between lithium titanate and Indian reduced activation ferritic-martensitic steel (In-RAFMS) was studied for the first time under ITER operating temperature. Lithium titanate required for the study was synthesized in-house. Coupons of In-RAFMS were packed inside lithium titanate powder and heated at 550 °C up to 900 h under inert argon atmosphere. The lithium titanate chemically reacted with ferritic martensitic steel to form a brittle and non-adherent oxide layer. The layer grew in a parabolic manner as a function of heating time. Microstructural and phase evolution of this oxide layer was studied using XRD, SEM and EPMA. Iron and chromium enriched zones were found within the oxide layer. Diffusion of oxygen (from Li_2TiO_3) appears to be controlling the oxide layer.

Mechanisms of impurity diffusion in rutile

International Nuclear Information System (INIS)

Peterson, N.L.; Sasaki, J.

1984-01-01

Tracer diffusion of 46 Sc, 51 Cr, 54 Mn, 59 Fe, 60 Co, 63 Ni, and 95 Zr, was measured as functions of crystal orientation, temperature, and oxygen partial pressure in rutile single crystals using the radioactive tracer sectioning technique. Compared to cation self-diffusion, divalent impurities (e.g., Co and Ni) diffuse extremely rapidly in TiO 2 and exhibit a large anisotropy in the diffusion behavior; divalent-impurity diffusion parallel to the c-axis is much larger than it is perpendicular to the c-axis. The diffusion of trivalent impurity ions (Sc and Cr) and tetravalent impurity ions (Zr) is similar to cation self-diffusion, as a function of temperature and of oxygen partial pressure. The divalent impurity ions Co and Ni apparently diffuse as interstitial ions along open channels parallel to the c-axis. The results suggest that Sc, Cr, and Zr ions diffuse by an interstitialcy mechanism involving the simultaneous and cooperative migration of tetravalent interstitial titanium ions and the tracer-impurity ions. Iron ions diffused both as divalent and as trivalent ions. 8 figures

Role of N2 molecules in pulse discharge production of I atoms for a pulsed chemical oxygen-iodine laser

International Nuclear Information System (INIS)

Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

2011-01-01

A pulsed electric discharge is the most effective means to turn chemical oxygen-iodine laser (COIL) operation into the pulse mode by fast production of iodine atoms. Experimental studies and numerical simulations are performed on a pulsed COIL initiated by an electric discharge in a mixture CF 3 I : N 2 : O 2 ( 3 X) : O 2 (a 1 Δ g ) flowing out of a chemical singlet oxygen generator. A transverse pulsed discharge is realized at various iodide pressures. The model comprises a system of kinetic equations for neutral and charged species, the electric circuit equation, the gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are repeatedly re-calculated by the electron Boltzmann equation solver when the plasma parameters are changed. The processes accounted for in the Boltzmann equation include direct and stepwise excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions and second-kind collisions. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. A conclusion is drawn about satisfactory agreement between the theory and the experiment.

Ionic Diffusion and Kinetic Homogeneous Chemical Reactions in the Pore Solution of Porous Materials with Moisture Transport

DEFF Research Database (Denmark)

Johannesson, Björn

2009-01-01

Results from a systematic continuum mixture theory will be used to establish the governing equations for ionic diffusion and chemical reactions in the pore solution of a porous material subjected to moisture transport. The theory in use is the hybrid mixture theory (HMT), which in its general form......’s law of diffusion and the generalized Darcy’s law will be used together with derived constitutive equations for chemical reactions within phases. The mass balance equations for the constituents and the phases together with the constitutive equations gives the coupled set of non-linear differential...... general description of chemical reactions among constituents is described. The Petrov – Galerkin approach are used in favour of the standard Galerkin weighting in order to improve the solution when the convective part of the problem is dominant. A modified type of Newton – Raphson scheme is derived...

Isotopic labeling study of oxygen diffusion in amorphous LaScO3 high-κ films on Si(100) and its effects on the electrical characteristics

International Nuclear Information System (INIS)

Lopes, J.M.J.; Littmark, U.; Roeckerath, M.; Durgun Oezben, E.; Lenk, S.; Schubert, J.; Mantl, S.; Breuer, U.; Besmehn, A.; Staerk, A.; Grande, P.L.; Sortica, M.A.; Radtke, C.

2009-01-01

The influence of post-deposition oxygen anneals on the properties of amorphous LaScO 3 films on Si(100) is reported. The use of an isotopically ( 18 O 2 ) enriched atmosphere allowed to investigate the 16 O- 18 O exchange and the oxygen diffusion across the dielectric layer. Such effects are connected to the formation of an interfacial layer. Oxygen annealing leads to nearly ideal capacitance-voltage curves, lower leakage currents and interface trap densities, as well as to κ-values up to 33 for the LaScO 3 films. These results are attributed to the suppression of oxygen-related trap centers and the achievement of a stoichiometric oxygen content. (orig.)

Oxygen configurations in silica

International Nuclear Information System (INIS)

Chelikowsky, James R.; Chadi, D. J.; Binggeli, N.

2000-01-01

We propose a transition state for oxygen in silica. This state is produced by the insertion of an oxygen molecule into the Si-O-Si bond, i.e., it consists of producing a Si-O-O-O-Si bond. This state allows molecular oxygen diffusion in silica without breaking the molecular O 2 bond and it is energetically more stable than a peroxy configuration. This configuration may allow for exchange of molecular oxygen with the oxygen in the silica framework. (c) 2000 The American Physical Society

Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes

Institute of Scientific and Technical Information of China (English)

ZAYAS Pérez Teresa; GEISSLER Gunther; HERNANDEZ Fernando

2007-01-01

The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculatio and advanced oxidation processes(AOP)had been studied.The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H202,UVO3 and UV/H-H202/O3 processes was determined under acidic conditions.For each of these processes,different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater.Coffee wastewater is characterized by a high chemical oxygen demand(COD)and low total suspended solids.The outcomes of coffee wastewater reeatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD,color,and turbidity.It was found that a reductiOn in COD of 67%could be realized when the coffee wastewater was treated by chemical coagulation-flocculatlon witll lime and coagulant T-1.When coffee wastewater was treated by coagulation-flocculation in combination with UV/H202,a COD reduction of 86%was achieved,although only after prolonged UV irradiation.Of the three advanced oxidation processes considered,UV/H202,uv/03 and UV/H202/03,we found that the treatment with UV/H2O2/O3 was the most effective,with an efficiency of color,turbidity and further COD removal of 87%,when applied to the flocculated coffee wastewater.

Intra-particle oxygen diffusion limitation in solid-state fermentation

NARCIS (Netherlands)

Oostra, J.; Comte, le E.P.; Heuvel, van den J.C.; Tramper, J.; Rinzema, A.

2001-01-01

Oxygen limitation in solid-state fermentation (SSF) has been the topic of modeling studies, but thus far, there has been no experimental elucidation on oxygen-transfer limitation at the particle level. Therefore, intra-particle oxygen transfer was experimentally studied in cultures of Rhizopus

Comparative evaluation of diffusion hypoxia and psychomotor skills with or without postsedation oxygenation following administration of nitrous oxide in children undergoing dental procedures: A clinical study

Directory of Open Access Journals (Sweden)

Vineet Inder Singh Khinda

2016-01-01

Full Text Available Background: Diffusion hypoxia is the most serious potential complication associated with nitrous oxide. It occurs during the recovery period. Hence, administration of 100% oxygen is mandatory as suggested by many authors. Aim: The aim of this study is to evaluate the occurrence/nonoccurrence of diffusion hypoxia in two groups of patients undergoing routine dental treatment under nitrous oxide sedation when one group is subjected to 7 min of postsedation oxygenation and the second group of the patients is made to breathe room air for the similar period. Materials and Methods: A total of sixty patients within the age group of 7–10 years requiring invasive dental procedures were randomly divided into two groups of 30 each using chit method. In the control group, patients were administered 100% oxygen postsedation, whereas, in the study group, patients were made to breathe room air postsedation. Various parameters (pulse rate, respiratory rate, blood pressure, and oxygen saturation [SpO2] were recorded pre- and post-operatively. Data were collected and then sent for statistical analysis. Results: The mean postoperative SpO2 at measurement times 1, 3, 5, and 7 min in both the groups was higher than the mean preoperative SpO2. This increase was statistically significant. No significant difference was found between the Trieger test scores. Conclusion: This study proves that clinical occurrence of diffusion hypoxia is not possible while following the routine procedure of nitrous oxide sedation.

Establishment and intra-/inter-laboratory validation of a standard protocol of reactive oxygen species assay for chemical photosafety evaluation.

Science.gov (United States)

Onoue, Satomi; Hosoi, Kazuhiro; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Matsuoka, Naoko; Nakamura, Kazuichi; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Seto, Yoshiki; Kato, Masashi; Yamada, Shizuo; Ohno, Yasuo; Kojima, Hajime

2013-11-01

A reactive oxygen species (ROS) assay was previously developed for photosafety evaluation of pharmaceuticals, and the present multi-center study aimed to establish and validate a standard protocol for ROS assay. In three participating laboratories, two standards and 42 coded chemicals, including 23 phototoxins and 19 nonphototoxic drugs/chemicals, were assessed by the ROS assay according to the standardized protocol. Most phototoxins tended to generate singlet oxygen and/or superoxide under UV-vis exposure, but nonphototoxic chemicals were less photoreactive. In the ROS assay on quinine (200 µm), a typical phototoxic drug, the intra- and inter-day precisions (coefficient of variation; CV) were found to be 1.5-7.4% and 1.7-9.3%, respectively. The inter-laboratory CV for quinine averaged 15.4% for singlet oxygen and 17.0% for superoxide. The ROS assay on 42 coded chemicals (200 µm) provided no false negative predictions upon previously defined criteria as compared with the in vitro/in vivo phototoxicity, although several false positives appeared. Outcomes from the validation study were indicative of satisfactory transferability, intra- and inter-laboratory variability, and predictive capacity of the ROS assay. Copyright © 2012 John Wiley & Sons, Ltd.

The change of longitudinal relaxation rate in oxygen enhanced pulmonary MRI depends on age and BMI but not diffusing capacity of carbon monoxide in healthy never-smokers.

Directory of Open Access Journals (Sweden)

Simon Sven Ivan Kindvall

Full Text Available Oxygen enhanced pulmonary MRI is a promising modality for functional lung studies and has been applied to a wide range of pulmonary conditions. The purpose of this study was to characterize the oxygen enhancement effect in the lungs of healthy, never-smokers, in light of a previously established relationship between oxygen enhancement and diffusing capacity of carbon monoxide in the lung (DL,CO in patients with lung disease.In 30 healthy never-smoking volunteers, an inversion recovery with gradient echo read-out (Snapshot-FLASH was used to quantify the difference in longitudinal relaxation rate, while breathing air and 100% oxygen, ΔR1, at 1.5 Tesla. Measurements were performed under multiple tidal inspiration breath-holds.In single parameter linear models, ΔR1 exhibit a significant correlation with age (p = 0.003 and BMI (p = 0.0004, but not DL,CO (p = 0.33. Stepwise linear regression of ΔR1 yields an optimized model including an age-BMI interaction term.In this healthy, never-smoking cohort, age and BMI are both predictors of the change in MRI longitudinal relaxation rate when breathing oxygen. However, DL,CO does not show a significant correlation with the oxygen enhancement. This is possibly because oxygen transfer in the lung is not diffusion limited at rest in healthy individuals. This work stresses the importance of using a physiological model to understand results from oxygen enhanced MRI.

Chemical interaction of fresh and saline waters with compacted bentonite

International Nuclear Information System (INIS)

Muurinen, A.; Lehikoinen, J.; Melamed, A.; Pitkaenen, P.

1996-01-01

The interaction of compacted sodium bentonite with fresh and saline ground-water simulant was studied. The parameters varied in the experiments were the compositions of the solutions and oxygen and carbon dioxide content in the surroundings. The main interests of the study were the chemical changes in the experimental solution, bentonite porewater and bentonite together with the microstructural properties of bentonite. The major processes with fresh water were the diffusion of sodium, potassium, sulphate, bicarbonate and chloride from bentonite to the solution, and the diffusion of calcium and magnesium from the solution into bentonite. The major processes in the experiments with saline water were the diffusion of the sodium, magnesium, sulphate and bicarbonate from bentonite into the solution, and the diffusion of calcium from the solution into bentonite

Preliminary analyses on hydrogen diffusion through small break of thermo-chemical IS process hydrogen plant

International Nuclear Information System (INIS)

Somolova, Marketa; Terada, Atsuhiko; Takegami, Hiroaki; Iwatsuki, Jin

2008-12-01

Japan Atomic Energy Agency has been conducting a conceptual design study of nuclear hydrogen demonstration plant, that is, a thermal-chemical IS process hydrogen plant coupled with the High temperature Engineering Test Reactor (HTTR-IS), which will be planed to produce a large amount of hydrogen up to 1000m 3 /h. As part of the conceptual design work of the HTTR-IS system, preliminary analyses on small break of a hydrogen pipeline in the IS process hydrogen plant was carried out as a first step of the safety analyses. This report presents analytical results of hydrogen diffusion behaviors predicted with a CFD code, in which a diffusion model focused on the turbulent Schmidt number was incorporated. By modifying diffusion model, especially a constant accompanying the turbulent Schmidt number in the diffusion term, analytical results was made agreed well with the experimental results. (author)

A theoretical model for the effects of reduced hemoglobin-oxygen affinity on tumor oxygenation

International Nuclear Information System (INIS)

Kavanagh, Brian D.; Secomb, Timothy W.; Hsu, Richard; Lin, P.-S.; Venitz, Jurgen; Dewhirst, Mark W.

2002-01-01

Purpose: To develop a theoretical model for oxygen delivery to tumors, and to use the model to simulate the effects of changing the affinity of hemoglobin for oxygen on tumor oxygenation. Methods and Materials: Hemoglobin affinity is expressed in terms of P 50 , the partial pressure of oxygen (Po 2 ) at half saturation. Effects of changing P 50 on arterial Po 2 are predicted using an effective vessel approach to describe diffusive oxygen transport in the lungs, assuming fixed systemic oxygen demand and fixed blood flow rate. The decline in oxygen content of blood as it flows through normal tissue before entering the tumor region is assumed fixed. The hypoxic fraction of the tumor region is predicted using a three-dimensional simulation of diffusion from a network of vessels whose geometry is derived from observations of tumor microvasculature in the rat. Results: In air-breathing rats, predicted hypoxic fraction decreases with moderate increases in P 50 , but increases with further increases of P 50 , in agreement with previous experimental results. In rats breathing hyperoxic gases, and in humans breathing either normoxic or hyperoxic gases, increased P 50 is predicted to improve tumor oxygenation. Conclusions: The results support the administration of synthetic agents to increase P 50 during radiation treatment of tumors

An improved oxygen diffusion model to explain the effect of low-temperature baking on high field losses in niobium superconducting cavities

Energy Technology Data Exchange (ETDEWEB)

Ciovati, Gianluigi

2006-07-01

Radio-frequency (RF) superconducting cavities made of high purity niobium are widely used to accelerate charged particle beams in particle accelerators. The major limitation to achieve RF field values approaching the theoretical limit for niobium is represented by ''anomalous'' losses which degrade the quality factor of the cavities starting at peak surface magnetic fields of about 100 mT, in absence of field emission. These high field losses are often referred to as ''Q-drop''. It has been observed that the Q-drop is drastically reduced by baking the cavities at 120 C for about 48 h under ultrahigh vacuum. An improved oxygen diffusion model for the niobium-oxide system is proposed to explain the benefit of the low-temperature baking on the Q-drop in niobium superconducting rf cavities. The model shows that baking at 120 C for 48 h allows oxygen to diffuse away from the surface, and therefore increasing the lower critical field towards the value for pure niobium.

Insights into thermal diffusion of germanium and oxygen atoms in HfO2/GeO2/Ge gate stacks and their suppressed reaction with atomically thin AlOx interlayers

International Nuclear Information System (INIS)

Ogawa, Shingo; Asahara, Ryohei; Minoura, Yuya; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji; Sako, Hideki; Kawasaki, Naohiko; Yamada, Ichiko; Miyamoto, Takashi

2015-01-01

The thermal diffusion of germanium and oxygen atoms in HfO 2 /GeO 2 /Ge gate stacks was comprehensively evaluated by x-ray photoelectron spectroscopy and secondary ion mass spectrometry combined with an isotopic labeling technique. It was found that 18 O-tracers composing the GeO 2 underlayers diffuse within the HfO 2 overlayers based on Fick's law with the low activation energy of about 0.5 eV. Although out-diffusion of the germanium atoms through HfO 2 also proceeded at the low temperatures of around 200 °C, the diffusing germanium atoms preferentially segregated on the HfO 2 surfaces, and the reaction was further enhanced at high temperatures with the assistance of GeO desorption. A technique to insert atomically thin AlO x interlayers between the HfO 2 and GeO 2 layers was proven to effectively suppress both of these independent germanium and oxygen intermixing reactions in the gate stacks

Thermophysical properties and oxygen transport in (Thx,Pu1-x)O2.

Science.gov (United States)

Galvin, C O T; Cooper, M W D; Rushton, M J D; Grimes, R W

2016-10-31

Using Molecular Dynamics, this paper investigates the thermophysical properties and oxygen transport of (Th x ,Pu 1-x )O 2 (0 ≤ x ≤ 1) between 300-3500 K. In particular, the superionic transition is investigated and viewed via the thermal dependence of lattice parameter, linear thermal expansion coefficient, enthalpy and specific heat at constant pressure. Oxygen diffusivity and activation enthalpy are also investigated. Below the superionic temperature an increase of oxygen diffusivity for certain compositions of (Th x ,Pu 1-x )O 2 compared to the pure end members is predicted. Oxygen defect formation enthalpies are also examined, as they underpin the superionic transition temperature and the increase in oxygen diffusivity. The increase in oxygen diffusivity for (Th x ,Pu 1-x )O 2 is explained in terms of lower oxygen defect formation enthalpies for (Th x ,Pu 1-x )O 2 than PuO 2 and ThO 2 , while links are drawn between the superionic transition temperature and oxygen Frenkel disorder.

Improvement of Hyperemic Myocardial Oxygen Extraction Fraction Estimation By A Diffusion Prepared Sequence

Science.gov (United States)

McCommis, Kyle S.; Koktzoglou, Ioannis; Zhang, Haosen; Goldstein, Thomas A.; Northrup, Benjamin E.; Li, Debiao; Gropler, Robert J.; Zheng, Jie

2010-01-01

Myocardial oxygen extraction fraction (OEF) during hyperemia can be estimated using a double-inversion-recovery (DIR) prepared T2-weighted black-blood sequence. Severe irregular ECG-triggering due to elevated heart rate and/or arrhythmias may render it difficult to adequately suppress the flowing left ventricle blood signal and thus potentially cause errors in the estimates of myocardial OEF. Thus, the goal of this study was to evaluate another black-blood technique, a diffusion-weighted (DW)-prepared TSE sequence for its ability to determine regional myocardial OEF during hyperemia. Control dogs and dogs with acute coronary artery stenosis were imaged with both the DIR- and DW-prepared TSE sequences at rest and during either dipyridamole or dobutamine hyperemia. Validation of MRI OEF estimates was performed using blood sampling from the artery and coronary sinus in control dogs. The two methods showed comparable correlations with blood sampling results (R2 = 0.9). Similar OEF estimations for all dogs were observed except for the group of dogs with severe coronary stenosis during dobutamine stress. In these dogs, the DW method provided more physiologically reasonable OEF (hyperemic OEF = 0.75 ± 0.08 vs resting OEF of 0.6) than the DIR method (hyperemic OEF = 0.56 ± 0.10). DW-preparation may be a valuable alternative for more accurate oxygenation measurements during irregular ECG-triggering. PMID:20512871

Implicit coupling of turbulent diffusion with chemical reaction mechanisms for prognostic atmospheric dispersion models

Energy Technology Data Exchange (ETDEWEB)

Berlowitz, D.R.

1996-11-01

In the last few decades the negative impact by humans on the thin atmospheric layer enveloping the earth, the basis for life on this planet, has increased steadily. In order to halt, or at least slow down this development, the knowledge and study of these anthropogenic influence has to be increased and possible remedies have to be suggested. An important tool for these studies are computer models. With their help the atmospheric system can be approximated and the various processes, which have led to the current situation can be quantified. They also serve as an instrument to assess short or medium term strategies to reduce this human impact. However, to assure efficiency as well as accuracy, a careful analysis of the numerous processes involved in the dispersion of pollutants in the atmosphere is called for. This should help to concentrate on the essentials and also prevent excessive usage of sometimes scarce computing resources. The basis of the presented work is the EUMAC Zooming Model (ETM), and particularly the component calculating the dispersion of pollutants in the atmosphere, the model MARS. The model has two main parts: an explicit solver, where the advection and the horizontal diffusion of pollutants are calculated, and an implicit solution mechanism, allowing the joint computation of the change of concentration due to chemical reactions, coupled with the respective influence of the vertical diffusion of the species. The aim of this thesis is to determine particularly the influence of the horizontal components of the turbulent diffusion on the existing implicit solver of the model. Suggestions for a more comprehensive inclusion of the full three dimensional diffusion operator in the implicit solver are made. This is achieved by an appropriate operator splitting. A selection of numerical approaches to tighten the coupling of the diffusion processes with the calculation of the applied chemical reaction mechanisms are examined. (author) figs., tabs., refs.

Oxygen, water, and sodium chloride transport in soft contact lenses materials.

Science.gov (United States)

Gavara, Rafael; Compañ, Vicente

2017-11-01

Oxygen permeability, diffusion coefficient of the sodium ions and water flux and permeability in different conventional hydrogel (Hy) and silicone-hydrogel (Si-Hy) contact lenses have been measured experimentally. The results showed that oxygen permeability and transmissibility requirements of the lens have been addressed through the use of siloxane containing hydrogels. In general, oxygen and sodium chloride permeability values increased with the water content of the lens but there was a percolation phenomenon from a given value of water uptake mainly in the Si-Hy lenses which appeared to be related with the differences between free water and bound water contents. The increase of ion permeability with water content did not follow a unique trend indicating a possible dependence of the chemical structure of the polymer and character ionic and non-ionic of the lens. Indeed, the salt permeability values for silicone hydrogel contact lenses were one order of magnitude below those of conventional hydrogel contact lenses, which can be explained by a diffusion of sodium ions occurring only through the hydrophilic channels. The increase of the ionic permeability in Si-Hy materials may be due to the confinement of ions in nanoscale water channels involving possible decreased degrees of freedom for diffusion of both water and ions. In general, ionic lenses presented values of ionic permeability and diffusivity higher than most non-ionic lenses. The tortuosity of the ionic lenses is lower than the non-ionic Si-Hy lenses. Frequency 55 and PureVision exhibited the highest water permeability and flux values and, these parameters were greater for ionic Si-Hy lenses than for ionic conventional hydrogel lenses. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2218-2231, 2017. © 2016 Wiley Periodicals, Inc.

Mathematical model of phase transformations in thermo-chemical cathodes with zirconium insertion

International Nuclear Information System (INIS)

Kavokin, A.A.; Kazmi, I.H.

2007-01-01

The mathematical model of thermo-chemical processes in the cathode of plasmatron working in the gas environment is investigated. The model describes electromagnetic, temperature and concentration fields taking into account kinetic of phase transformation and chemical reaction in accordance with a state diagram. The offered approach is simpler than the Stefan's approach of describing an analogical phase transformation. As an example the case of copper cathodes with the zirconium insertion in the environment of oxygen is considered. The influence of separate parts of process on distribution of temperature inside of the insertion is estimated. On the basis of this analysis the opportunity of use of stationary approach for electric and temperature fields is shown and analytical formulas for temperature are received. After that a numerical solution for gas concentration distribution is obtained. The calculations on the specified model show that the size of area of a phase zirconium oxides depends mainly upon coefficient of diffusion of oxygen. The calculations for various types of dependencies of gas diffusion coefficient from temperature are concluded. The results of calculations develop understanding of some features of oxidation process of a zirconium insertion. Typical example of multi phase process model is the mathematical description of a heat and mass transfer occurring in metal which is being heated by an electric arch in the gas medium (1, 2, 4). The macroscopic model of physical and chemical transformations can be described as follows (3). As a metal is heated on the surface of an electrode as a function of rising results in the border dividing solid and liquid phases moves ahead deep into the electrode. At the same time there is a diffusion of gas in electrode and formation of new chemical compounds which can noticeably differ in the physical and chemical properties from each other and metal of the electrode. Moreover we shall name a phase of substance not

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

Science.gov (United States)

Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

2015-01-01

The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

CaMn0.875Ti0.125O3 as oxygen carrier for chemical-looping combustion with oxygen uncoupling (CLOU)—Experiments in a continuously operating fluidized-bed reactor system

KAUST Repository

Rydén, Magnus

2011-03-01

Particles of the perovskite material CaMn0.875Ti0.125O3 has been examined as oxygen carrier for chemical-looping with oxygen uncoupling, and for chemical-looping combustion of natural gas, by 70h of experiments in a circulating fluidized-bed reactor system. For the oxygen uncoupling experiments, it was found that the particles released O2 in gas phase at temperatures above 720°C when the fuel reactor was fluidized with CO2. The effect increased with increased temperature, and with the O2 partial pressure in the air reactor. At 950°C, the O2 concentration in the outlet from the fuel reactor was in the order of 4.0vol%, if the particles were oxidized in air. For the chemical-looping combustion experiments the combustion efficiency with standard process parameters was in the order of 95% at 950°C, using 1000kg oxygen carrier per MW natural gas, of which about 30% was located in the fuel reactor. Reducing the fuel flow so that 1900kg oxygen carrier per MW natural gas was used improved the combustion efficiency to roughly 99.8%. The particles retained their physical properties, reactivity with CH4 and ability to release gas-phase O2 reasonably well throughout the testing period and there were no problems with the fluidization or formation of solid carbon in the reactor. X-ray diffraction showed that the particles underwent changes in their phase composition though. © 2010 Elsevier Ltd.

Noninvasive diffuse optical monitoring of head and neck tumor blood flow and oxygenation during radiation delivery

Science.gov (United States)

Dong, Lixin; Kudrimoti, Mahesh; Cheng, Ran; Shang, Yu; Johnson, Ellis L.; Stevens, Scott D.; Shelton, Brent J.; Yu, Guoqiang

2012-01-01

This study explored using a novel diffuse correlation spectroscopy (DCS) flow-oximeter to noninvasively monitor blood flow and oxygenation changes in head and neck tumors during radiation delivery. A fiber-optic probe connected to the DCS flow-oximeter was placed on the surface of the radiologically/clinically involved cervical lymph node. The DCS flow-oximeter in the treatment room was remotely operated by a computer in the control room. From the early measurements, abnormal signals were observed when the optical device was placed in close proximity to the radiation beams. Through phantom tests, the artifacts were shown to be caused by scattered x rays and consequentially avoided by moving the optical device away from the x-ray beams. Eleven patients with head and neck tumors were continually measured once a week over a treatment period of seven weeks, although there were some missing data due to the patient related events. Large inter-patient variations in tumor hemodynamic responses were observed during radiation delivery. A significant increase in tumor blood flow was observed at the first week of treatment, which may be a physiologic response to hypoxia created by radiation oxygen consumption. Only small and insignificant changes were found in tumor blood oxygenation, suggesting that oxygen utilizations in tumors during the short period of fractional radiation deliveries were either minimal or balanced by other effects such as blood flow regulation. Further investigations in a large patient population are needed to correlate the individual hemodynamic responses with the clinical outcomes for determining the prognostic value of optical measurements. PMID:22312579

Chemical segregation and self polarisation in ferroelectrics

Directory of Open Access Journals (Sweden)

Bernard E. Watts

2009-06-01

Full Text Available Chemical partitioning or segregation is commonly encountered in solid-state syntheses. It is driven by compositional, thermal and electric field gradients. These phenomena can be quite extreme in thin films and lead to notable effects on the electrical properties of ferroelectrics. The segregation in ferroelectric thin films will be illustrated and the mechanisms explained in terms of diffusion processes driven by a potential gradient of the oxygen. The hypothesis can also explain self polarisation and imprint in ferroelectric hysteresis.

Brownian motion in a field of force and the diffusion theory of chemical reactions. II

NARCIS (Netherlands)

Brinkman, H.C.

1956-01-01

H. A. Kramers has studied the rate of chemical reactions in view of the Brownian forces caused by a surrounding medium in temperature equilibrium. In a previous paper 3) the author gave a solution of Kramers' diffusion equation in phase space by systematic development. In this paper the general

Assessment of oxygen diffusion coefficients by studying high-temperature oxidation behaviour of Zr1Nb fuel cladding in the temperature range of 1100–1300 °C

Energy Technology Data Exchange (ETDEWEB)

Négyesi, M., E-mail: negy@seznam.cz [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Trojanova 13, 120 00 Praha 2 (Czech Republic); UJP PRAHA a.s., Nad Kamínkou 1345, 156 10 Praha – Zbraslav (Czech Republic); Chmela, T. [UJP PRAHA a.s., Nad Kamínkou 1345, 156 10 Praha – Zbraslav (Czech Republic); Veselský, T. [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Trojanova 13, 120 00 Praha 2 (Czech Republic); Krejčí, J. [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Trojanova 13, 120 00 Praha 2 (Czech Republic); CHEMCOMEX Praha a.s., Elišky Přemyslovny 379, 156 10 Praha – Zbraslav (Czech Republic); Novotný, L.; Přibyl, A. [UJP PRAHA a.s., Nad Kamínkou 1345, 156 10 Praha – Zbraslav (Czech Republic); Bláhová, O. [New Technologies Research Centre, University of West Bohemia, Univerzitní 8, 306 14 Plzeň (Czech Republic); Burda, J. [NRI Rez plc, Husinec-Řež 130, 250 68 Řež (Czech Republic); Siegl, J. [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Trojanova 13, 120 00 Praha 2 (Czech Republic); Vrtílková, V. [UJP PRAHA a.s., Nad Kamínkou 1345, 156 10 Praha – Zbraslav (Czech Republic)

2015-01-15

The paper deals with high-temperature steam oxidation behaviour of Zr1Nb fuel cladding. First of all, comprehensive experimental program was conducted to provide sufficient experimental data, such as the thicknesses of evolved phase layers and the overall weight gain kinetics, as well as the oxygen concentration and nanohardness values at phase boundaries. Afterwards, oxygen diffusion coefficients in the oxide, in the α-Zr(O) layer, in the double-phase (α + β)-Zr region, and in the β-phase region have been estimated based on the experimental data employing analytical solution of the multiphase moving boundary problem, assuming the equilibrium conditions being fulfilled at the interface boundaries. Eventually, the determined oxygen diffusion coefficients served as input into the in-house numerical code, which was designed to predict the high-temperature oxidation behaviour of Zr1Nb fuel cladding. Very good agreement has been achieved between the numerical calculations and the experimental data.

Atomic oxygen adsorption and its effect on the oxidation behaviour of ZrB2-ZrC-SiC in air

International Nuclear Information System (INIS)

Gao Dong; Zhang Yue; Xu Chunlai; Song Yang; Shi Xiaobin

2011-01-01

Research highlights: → Atomic oxygen was adsorbed on the surface of ZrB 2 -ZrC-SiC ceramics. → Atomic oxygen was preferred reacted with borides according to XPS spectra. → The atomic oxygen adsorption is detrimental to the oxidation resistance. → The porosity should be the major reason which provides diffusion path for the atomic oxygen. → The structure evolution of the ceramics during oxidation is analyzed. - Abstract: Atomic oxygen is adsorbed on the surface of the hot-pressed ZrB 2 -ZrC-SiC ceramic composites, and then the ceramic composites are oxidized in air up to 1500 deg. C with the purpose of clarifying the effect of atomic oxygen adsorption on the oxidation behaviour of the ceramic composites. The XPS spectra are employed to identify the adsorption mechanism of atomic oxygen on the surface of the ceramic composites, and the formation of O-B, O-Zr, and O-Si bonds indicates that atomic oxygen is chemically adsorbed on the surface of the ceramic. In addition, atomic oxygen is preferred to be adsorbed on the surface of borides according to the Zr 3d core level spectrum. On the other hand, the atomic oxygen adsorption is detrimental to the oxidation resistance according to experimental results, and the porosity of the ceramic should be the major reason which provides diffusion path for the atomic oxygen. Furthermore, the structure evolution of the ceramic composites during oxidation process is analyzed.

Study of dimensional changes during redox cycling of oxygen carrier materials for chemical looping combustion

NARCIS (Netherlands)

Fossdal, A.; Darell, O.; Lambert, A.; Schols, E.; Comte, E.; Leenman, R.N.; Blom, R.

2015-01-01

Dimensional and phase changes of four candidate oxygen carrier materials for chemical looping combustion are investigated by dilatometry and high-temperature X-ray diffraction during four redox cycles. NiO/Ni2AlO4 does not exhibit significant dimensional changes during cycling, and it is shown that

About the Role of the Bottleneck/Cork Interface on Oxygen Transfer.

Science.gov (United States)

Lagorce-Tachon, Aurélie; Karbowiak, Thomas; Paulin, Christian; Simon, Jean-Marc; Gougeon, Régis D; Bellat, Jean-Pierre

2016-09-07

The transfer of oxygen through a corked bottleneck was investigated using a manometric technique. First, the effect of cork compression on oxygen transfer was evaluated without considering the glass/cork interface. No significant effect of cork compression (at 23% strain, corresponding to the compression level of cork in a bottleneck for still wines) was noticeable on the effective diffusion coefficient of oxygen. The mean value of the effective diffusion coefficient is equal to 10(-8) m(2) s(-1), with a statistical distribution ranging from 10(-10) to 10(-7) m(2) s(-1), which is of the same order of magnitude as for the non-compressed cork. Then, oxygen transfer through cork compressed in a glass bottleneck was determined to assess the effect of the glass/cork interface. In the particular case of a gradient-imposed diffusion of oxygen through our model corked bottleneck system (dry cork without surface treatment; 200 and ∼0 hPa of oxygen on both sides of the sample), the mean effective diffusion coefficient is of 5 × 10(-7) m(2) s(-1), thus revealing the possible importance of the role of the glass/stopper interface in the oxygen transfer.

Oxygen Concentration Inside a Functioning Photosynthetic Cell

OpenAIRE

Kihara, Shigeharu; Hartzler, Daniel A.; Savikhin, Sergei

2014-01-01

The excess oxygen concentration in the photosynthetic membranes of functioning oxygenic photosynthetic cells was estimated using classical diffusion theory combined with experimental data on oxygen production rates of cyanobacterial cells. The excess oxygen concentration within the plesiomorphic cyanobacterium Gloeobactor violaceus is only 0.025 μM, or four orders of magnitude lower than the oxygen concentration in air-saturated water. Such a low concentration suggests that the first oxygenic...

Application and further development of diffusion based 2D chemical imaging techniques in the rhizosphere

Science.gov (United States)

Hoefer, Christoph; Santner, Jakob; Borisov, Sergey; Kreuzeder, Andreas; Wenzel, Walter; Puschenreiter, Markus

2015-04-01

Two dimensional chemical imaging of root processes refers to novel in situ methods to investigate and map solutes at a high spatial resolution (sub-mm). The visualization of these solutes reveals new insights in soil biogeochemistry and root processes. We derive chemical images by using data from DGT-LA-ICP-MS (Diffusive Gradients in Thin Films and Laser Ablation Inductively Coupled Plasma Mass Spectrometry) and POS (Planar Optode Sensors). Both technologies have shown promising results when applied in aqueous environment but need to be refined and improved for imaging at the soil-plant interface. Co-localized mapping using combined DGT and POS technologies and the development of new gel combinations are in our focus. DGTs are smart and thin (hydrogels; containing a binding resin for the targeted analytes (e.g. trace metals, phosphate, sulphide or radionuclides). The measurement principle is passive and diffusion based. The present analytes are diffusing into the gel and are bound by the resin. Thereby, the resin acts as zero sink. After application, DGTs are retrieved, dried, and analysed using LA-ICP-MS. The data is then normalized by an internal standard (e.g. 13C), calibrated using in-house standards and chemical images of the target area are plotted using imaging software. POS are, similar to DGT, thin sensor foils containing a fluorophore coating depending on the target analyte. The measurement principle is based on excitation of the flourophore by a specific wavelength and emission of the fluorophore depending on the presence of the analyte. The emitted signal is captured using optical filters and a DSLR camera. While DGT analysis is destructive, POS measurements can be performed continuously during the application. Both semi-quantitative techniques allow an in situ application to visualize chemical processes directly at the soil-plant interface. Here, we present a summary of results from rhizotron experiments with different plants in metal contaminated and

Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

Science.gov (United States)

Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

2018-03-01

Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

Thermophysical properties and oxygen transport in (Thx,Pu1−x)O2

Science.gov (United States)

Galvin, C. O. T.; Cooper, M. W. D.; Rushton, M. J. D.; Grimes, R. W.

2016-01-01

Using Molecular Dynamics, this paper investigates the thermophysical properties and oxygen transport of (Thx,Pu1−x)O2 (0 ≤ x ≤ 1) between 300–3500 K. In particular, the superionic transition is investigated and viewed via the thermal dependence of lattice parameter, linear thermal expansion coefficient, enthalpy and specific heat at constant pressure. Oxygen diffusivity and activation enthalpy are also investigated. Below the superionic temperature an increase of oxygen diffusivity for certain compositions of (Thx,Pu1−x)O2 compared to the pure end members is predicted. Oxygen defect formation enthalpies are also examined, as they underpin the superionic transition temperature and the increase in oxygen diffusivity. The increase in oxygen diffusivity for (Thx,Pu1−x)O2 is explained in terms of lower oxygen defect formation enthalpies for (Thx,Pu1−x)O2 than PuO2 and ThO2, while links are drawn between the superionic transition temperature and oxygen Frenkel disorder. PMID:27796314

Vibrationally Excited Carbon Monoxide Produced via a Chemical Reaction Between Carbon Vapor and Oxygen

Science.gov (United States)

Jans, Elijah R.; Eckert, Zakari; Frederickson, Kraig; Rich, Bill; Adamovich, Igor V.

2017-06-01

Measurements of the vibrational distribution function of carbon monoxide produced via a reaction between carbon vapor and molecular oxygen has shown a total population inversion on vibrational levels 4-7. Carbon vapor, produced using an arc discharge to sublimate graphite, is mixed with an argon oxygen flow. The excited carbon monoxide is vibrationally populated up to level v=14, at low temperatures, T=400-450 K, in a collision-dominated environment, 15-20 Torr, with total population inversions between v=4-7. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of the reaction enthalpy. Kinetic modeling of the flow reactor, including state specific vibrational processes, was performed to infer the vibrational distribution of the products of the reaction. The results show viability of developing of a new chemical CO laser from the reaction of carbon vapor and oxygen.

Cytotoxicity But No Mutagenicity In Bacteria With Externally Generated Singlet Oxygen

Science.gov (United States)

Midden, W. Robert; Dahl, Thomas A.; Hartman, Philip E.

1988-02-01

Singlet oxygen is believed to be an important intermediate responsible for the cytotoxicity of HpD phototherapy. It has been recognized as a possible intermediate in photosensitization for more than 20 years. However, it has been difficult to obtain conclusive evidence of its biological characteristics in the past because most of the methods available for its generation that are compatible with biological systems also generate other reactive intermediates whose effects are difficult to distinguish from singlet oxygen. We have used a recently devised separated-surface-sensi-tizer (S-S-S) system for singlet oxygen generation' to measure the cytotoxicity and mutagenicity of singlet oxygen in bacteria. The S-S-S system employs rose bengal as a sensitizer immobilized on one surface of a glass plate. The glass plate is placed sensitizer-side down a small distance (plate is illuminated from above to generate singlet oxygen at the surface of the sensitizer. The singlet oxygen thus generated can diffuse the short dis-tance to the surface of the membrane to react with the bacteria. Because of the short lifetime of singlet oxygen in air, increasing the distance between the sensitizer and the membrane causes a decline in the amount of singlet oxygen reaching the membrane according to a function derived from the Einstein-Smoluchowski equation for net displacement by diffusion. Plotting the log of the effect measured (e.g., cytotoxicity) vs. the square of the distance gives a straight line. The slope of this line can be used to calculate the gas phase half life of the intermediate responsible for the observed effects. We have found that bacteria are rapidly killed in the illuminated S-S-S system and that the gas phase half life of the agent responsible for cell killing is the same as that of singlet oxygen. This observation and other simple chemical tests have conclusively estab-lished that singlet oxygen is responsible for the cytotoxicity observed with bacteria. Dosimetry

Relativistic thermodynamics of irreversible processes I. Heat conduction, diffusion, viscous flow and chemical reactions; formal part

NARCIS (Netherlands)

Kluitenberg, G.A.; Groot, S.R. de; Mazur, P.

1953-01-01

The relativistic thermodynamics of irreversible processes is developed for an isotropic mixture in which heat conduction, diffusion, viscous flow, chemical reactions and their cross-phenomena may occur. The four-vectors, representing the relative flows of matter, are defined in such a way that, in

Generation of atomic iodine via fluorine for chemical oxygen-iodine laser

International Nuclear Information System (INIS)

Jirasek, Vit; Spalek, Otomar; Censky, Miroslav; Pickova, Irena; Kodymova, Jarmila; Jakubec, Ivo

2007-01-01

A method of the chemical generation of atomic iodine for a chemical oxygen-iodine laser (COIL) using atomic fluorine as a reaction intermediate was studied experimentally. This method is based on the reaction between F 2 and NO providing F atoms, and the reaction of F with HI resulting in iodine atoms generation. Atomic iodine was produced with efficiency exceeding 40% relative to initial F 2 flow rate. This efficiency was nearly independent on pressure and total gas flow rate. The F atoms were stable in the reactor up to 2 ms. An optimum ratio of the reactants flow rates was F 2 :NO:HI = 1:1:1. A rate constant of the reaction of F 2 with HI was determined. The numerical modelling showed that remaining HI and IF were probably consumed in their mutual reaction. The reaction system was found suitable for employing in a generator of atomic iodine with its subsequent injection into a supersonic nozzle of a COIL

Contribution to the study of the interactions between residual stresses and oxygen dissolution in a reactive deformable solid

International Nuclear Information System (INIS)

Raceanu, Laura

2011-01-01

The aim of this PhD work is to highlight the interactions between the mechanical stress and the chemical composition within diffusion of matter process for a reactive solid. The chronological evolution of our work goes from a parametric numerical study to an experimental study and reveals the role of mechanical stresses on the oxygen diffusion process. Different origins of mechanical stress were first numerically analysed from the point of view of their impacts on the process of oxygen diffusion into a metal (Zr) or a ceramic (UO 2 ) subjected to an oxidizing environment. This approach allowed us: - to identify a surface treatment (shot-peening) able to generate a residual specific stress field, as a starting point for an experimental study implementation in order to validate the numerical study conclusions; - to highlight the ability of the stress field on the stabilisation of the morphology of an undulated metal/oxide interface (case of Zr). In the experimental approach, different techniques were used to characterize the material (GDOS, SEM, TGA, hole-drilling method, micro-hardness tests). They permitted the detection of a strong influence of shot-peening on the oxidation rate. The comparison of experimental and numerical simulation results reveals strong interactions between stress and compositions fields induced by the different treatments (shot-peening and/or pre-oxidation). This study opens up many opportunities in the understanding of multi-physics coupling effects being very useful for the optimization of mechanical and chemical surface-treatments, able furthermore to favour the diffusion (nitriding, cementation) or to slow it down (corrosion). (author) [fr

Osmotic phenomena in application for hyperbaric oxygen treatment.

Science.gov (United States)

Babchin, A; Levich, E; Melamed M D, Y; Sivashinsky, G

2011-03-01

Hyperbaric oxygen (HBO) treatment defines the medical procedure when the patient inhales pure oxygen at elevated pressure conditions. Many diseases and all injuries are associated with a lack of oxygen in tissues, known as hypoxia. HBO provides an effective method for fast oxygen delivery in medical practice. The exact mechanism of the oxygen transport under HBO conditions is not fully identified. The objective of this article is to extend the colloid and surface science basis for the oxygen transport in HBO conditions beyond the molecular diffusion transport mechanism. At a pressure in the hyperbaric chamber of two atmospheres, the partial pressure of oxygen in the blood plasma increases 10 times. The sharp increase of oxygen concentration in the blood plasma creates a considerable concentration gradient between the oxygen dissolved in the plasma and in the tissue. The concentration gradient of oxygen as a non-electrolyte solute causes an osmotic flow of blood plasma with dissolved oxygen. In other words, the molecular diffusion transport of oxygen is supplemented by the convective diffusion raised due to the osmotic flow, accelerating the oxygen delivery from blood to tissue. A non steady state equation for non-electrolyte osmosis is solved asymptotically. The solution clearly demonstrates two modes of osmotic flow: normal osmosis, directed from lower to higher solute concentrations, and anomalous osmosis, directed from higher to lower solute concentrations. The fast delivery of oxygen from blood to tissue is explained on the basis of the strong molecular interaction between the oxygen and the tissue, causing an influx of oxygen into the tissue by convective diffusion in the anomalous osmosis process. The transport of the second gas, nitrogen, dissolved in the blood plasma, is also taken into the consideration. As the patient does not inhale nitrogen during HBO treatment, but exhales it along with oxygen and carbon dioxide, the concentration of nitrogen in blood

Effects of normobaric versus hyperbaric oxygen on cell injury induced by oxygen and glucose deprivation in acute brain slices

Directory of Open Access Journals (Sweden)

Laurent Chazalviel

2016-01-01

Full Text Available Normobaric oxygen (NBO and hyperbaric oxygen (HBO are emerging as a possible co-treatment of acute ischemic stroke. Both have been shown to reduce infarct volume, to improve neurologic outcome, to promote endogenous tissue plasminogen activator-induced thrombolysis and cerebral blood flow, and to improve tissue oxygenation through oxygen diffusion in the ischemic areas, thereby questioning the interest of HBO compared to NBO. In the present study, in order to investigate and compare the oxygen diffusion effects of NBO and HBO on acute ischemic stroke independently of their effects at the vascular level, we used acute brain slices exposed to oxygen and glucose deprivation, an ex vivo model of brain ischemia that allows investigating the acute effects of NBO (partial pressure of oxygen (pO 2 = 1 atmospheres absolute (ATA = 0.1 MPa and HBO (pO 2 = 2.5 ATA = 0.25 MPa through tissue oxygenation on ischemia-induced cell injury as measured by the release of lactate dehydrogenase. We found that HBO, but not NBO, reduced oxygen and glucose deprivation-induced cell injury, indicating that passive tissue oxygenation (i.e. without vascular support of the brain parenchyma requires oxygen partial pressure higher than 1 ATA.

An investigation into the availability and role of oxygen gas in gold ...

African Journals Online (AJOL)

The oxygen content of tailings dams around the Witwatersrand Basin was quantitatively measured over a period of 2 months using a multi-level gas sampling device (MLGS) in an attempt to understand the diffusion of oxygen in tailings dams as a result of acid mine drainage. The measured oxygen showed that the diffusion ...

Thermal and mechanical behaviour of oxygen carrier materials for chemical looping combustion in a packed bed reactor

International Nuclear Information System (INIS)

Jacobs, M.; Van Noyen, J.; Larring, Y.; Mccann, M.; Pishahang, M.; Amini, S.; Ortiz, M.; Galluci, F.; Sint-Annaland, M.V.; Tournigant, D.; Louradour, E.; Snijkers, F.

2015-01-01

Highlights: • Ilmenite-based oxygen carriers were developed for packed-bed chemical looping. • Addition of Mn_2O_3 increased mechanical strength and microstructure of the carriers. • Oxygen carriers were able to withstand creep and thermal cycling up to 1200 °C. • Ilmenite-based granules are a promising shape for packed-bed reactor conditions. - Abstract: Chemical looping combustion (CLC) is a promising carbon capture technology where cyclic reduction and oxidation of a metallic oxide, which acts as a solid oxygen carrier, takes place. With this system, direct contact between air and fuel can be avoided, and so, a concentrated CO_2 stream is generated after condensation of the water in the exit gas stream. An interesting reactor system for CLC is a packed bed reactor as it can have a higher efficiency compared to a fluidized bed concept, but it requires other types of oxygen carrier particles. The particles must be larger to avoid a large pressure drop in the reactor and they must be mechanically strong to withstand the severe reactor conditions. Therefore, oxygen carriers in the shape of granules and based on the mineral ilmenite were subjected to thermal cycling and creep tests. The mechanical strength of the granules before and after testing was investigated by crush tests. In addition, the microstructure of these oxygen particles was studied to understand the relationship between the physical properties and the mechanical performance. It was found that the granules are a promising shape for a packed bed reactor as no severe degradation in strength was noticed upon thermal cycling and creep testing. Especially, the addition of Mn_2O_3 to the ilmenite, which leads to the formation of an iron–manganese oxide, seems to results in stronger granules than the other ilmenite-based granules.

Oxidative Corrosion of the UO ₂ (001) Surface by Nonclassical Diffusion

Energy Technology Data Exchange (ETDEWEB)

Stubbs, Joanne E.; Biwer, Craig A.; Chaka, Anne M. [Pacific Northwest; Ilton, Eugene S. [Pacific Northwest; Du, Yingge [Pacific Northwest; Bargar, John R. [Stanford Synchrotron; Eng, Peter J.

2017-11-07

Uranium oxide is central to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that during corrosion of the UO2 (111) surface under either 1 atm O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we present results from surface x-ray scattering that reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ~52 Å below the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy indicates U is present as U(IV), U(V), and U(VI).

Chemically abrupt interface between Ce oxide and Fe films

International Nuclear Information System (INIS)

Lee, H.G.; Lee, D.; Kim, S.; Kim, S.G.; Hwang, Chanyong

2005-01-01

A chemically abrupt Fe/Ce oxide interface can be formed by initial oxidation of an Fe film followed by deposition of Ce metal. Once a Ce oxide layer is formed on top of Fe, it acts a passivation barrier for oxygen diffusion. Further deposition of Ce metal followed by its oxidation preserve the abrupt interface between Ce oxide and Fe films. The Fe and Ce oxidation states have been monitored at each stage using X-ray photoelectron spectroscopy

The roles of resuspension, diffusion and biogeochemical processes on oxygen dynamics offshore of the Rhône River, France: a numerical modeling study

Science.gov (United States)

Moriarty, Julia M.; Harris, Courtney K.; Fennel, Katja; Friedrichs, Marjorie A. M.; Xu, Kehui; Rabouille, Christophe

2017-04-01

Observations indicate that resuspension and associated fluxes of organic material and porewater between the seabed and overlying water can alter biogeochemical dynamics in some environments, but measuring the role of sediment processes on oxygen and nutrient dynamics is challenging. A modeling approach offers a means of quantifying these fluxes for a range of conditions, but models have typically relied on simplifying assumptions regarding seabed-water-column interactions. Thus, to evaluate the role of resuspension on biogeochemical dynamics, we developed a coupled hydrodynamic, sediment transport, and biogeochemical model (HydroBioSed) within the Regional Ocean Modeling System (ROMS). This coupled model accounts for processes including the storage of particulate organic matter (POM) and dissolved nutrients within the seabed; fluxes of this material between the seabed and the water column via erosion, deposition, and diffusion at the sediment-water interface; and biogeochemical reactions within the seabed. A one-dimensional version of HydroBioSed was then implemented for the Rhône subaqueous delta in France. To isolate the role of resuspension on biogeochemical dynamics, this model implementation was run for a 2-month period that included three resuspension events; also, the supply of organic matter, oxygen, and nutrients to the model was held constant in time. Consistent with time series observations from the Rhône Delta, model results showed that erosion increased the diffusive flux of oxygen into the seabed by increasing the vertical gradient of oxygen at the seabed-water interface. This enhanced supply of oxygen to the seabed, as well as resuspension-induced increases in ammonium availability in surficial sediments, allowed seabed oxygen consumption to increase via nitrification. This increase in nitrification compensated for the decrease in seabed oxygen consumption due to aerobic remineralization that occurred as organic matter was entrained into the water

Estimation of grain boundary diffusivity in near-α titanium polycrystals

International Nuclear Information System (INIS)

Brockman, Robert A.; Pilchak, Adam L.; John Porter, W.; John, Reji

2011-01-01

The role of enhanced grain boundary diffusivity in high-temperature diffusion of interstitial elements through metals is widely recognized but poorly characterized in most materials. This paper summarizes an effort to estimate grain boundary diffusivity of oxygen in a near-α titanium alloy, Ti-6Al-2Sn-4Zr-2Mo-0.1Si, by explicitly incorporating microstructure obtained from electron backscatter diffraction into an analytical model. Attention is focused on near-surface diffusion behavior contributing to the rapid ingress of oxygen and possible crack initiation in high-temperature environments.

Diffusion of samarium into cobalt in the reduction-diffusion process

International Nuclear Information System (INIS)

Freitas Nogueira, P. de; Neto, F.B.; Landgraf, F.J.G.

1998-01-01

The presence of metallic cobalt in samarium-cobalt powders is a major cause for low magnetic properties in magnets. This paper intends to investigate the effect of time and temperature in the microstructure of powders produced by reduction-diffusion. This process, developed for the production of rare earth-transition metal alloys, consists on the reduction of the rare earth oxide with metallic calcium (or calcium hydride) and its subsequent diffusion into the cobalt particle. In the present work, a mixture of samarium oxide, cobalt powder and metallic calcium was heated to 1100 or 1200 C for 2 or 4 hours in a tubular furnace under one atmosphere of purified argon. The material thereof obtained, a sintered mass is disintegrated by aqueous crepitation. The powder was evaluated in terms of its chemical composition, its samarium yield and the intermetallic compounds present. The samarium, oxygen and calcium content of the powders produced were adequate for magnet production. However, despite the massive formation of the SmCo 5 compound after 2 hours at 1100 C, final homogeneity is attained only after 4 hours at 1200 C, with the presence of SmCo 5 and Sm 2 Co 7 and the absence of the Sm 5 Co 19 compound. Also, metallic cobalt and Sm 2 Co 17 were observed in the materials produced after 2 hours at 1100 or 1200 C. (orig.)

User's manual of BISHOP. A Bi-Phase, Sodium-Hydrogen-Oxygen system, chemical equilibrium calculation program

International Nuclear Information System (INIS)

Okano, Yasushi; Yamaguchi, Akira

2001-07-01

In an event of sodium leakage in liquid metal fast breeder reactors, liquid sodium flows out of piping, and droplet combustion might occur under a certain environmental condition. The combustion heat and reaction products should be evaluated in the sodium fire analysis codes for investigating the influence of the sodium leak age and fire incident. In order to analyze the reaction heat and products, the multi-phase chemical equilibrium calculation program for a sodium, oxygen and hydrogen system has been developed. The developed numerical program is named BISHOP, which denotes 'Bi-Phase, Sodium-Hydrogen-Oxygen, Chemical Equilibrium Calculation Program'. The Gibbs free energy minimization method is used because of the following advantages. Chemical species are easily added and changed. A variety of thermodynamic states, such as isothermal and isentropic changes, can be dealt with in addition to constant temperature and pressure processes. In applying the free energy minimization method to solve the multi-phase sodium reaction system, three new numerical calculation techniques are developed. One is theoretical simplification of phase description in equation system, the other is to extend the Gibbs free energy minimization method to a multi-phase system, and the last is to establish the efficient search for the minimum value. The reaction heat and products at the equilibrium state can be evaluated from the initial conditions, such as temperature, pressure and reactants, using BISHOP. This report describes the thermochemical basis of chemical equilibrium calculations, the system of equations, simplification models, and the procedure to prepare input data and usage of BISHOP. (author)

Erosion behaviour of physically vapour-deposited and chemically vapour-deposited SiC films coated on molybdenum during oxygenated argon beam thinning

International Nuclear Information System (INIS)

Shikama, T.; Kitajima, M.; Fukutomi, M.; Okada, M.

1984-01-01

The erosion behaviour during bombardment with a 5 keV argon beam at room temperature was studied for silicon carbide (SiC) films of thickness of about 10 μm coated on molybdenum by physical vapour deposition (PVD) and chemical vapour deposition (CVD). The PVD SiC (plasma-assisted ion plating) exhibited a greater thinning rate than the CVD SiC film. Electron probe X-ray microanalysis revealed that the chemical composition of PVD SiC was changed to a composition enriched in silicon by the bombardment, and there was a notable change in its surface morphology. The CVD SiC retained its initial chemical composition with only a small change in its surface morphology. Auger electron spectroscopy indicated that silicon oxide was formed on the surface of PVD SiC by the bombardment. The greater thinning rate and easier change in chemical composition in PVD SiC could be attributed to its readier chemical reaction with oxygen due to its more non-uniform structure and weaker chemical bonding. Oxygen was present as one of the impurities in the argon beam. (Auth.)

Modelling chemical abundance distributions for dwarf galaxies in the Local Group: the impact of turbulent metal diffusion

Science.gov (United States)

Escala, Ivanna; Wetzel, Andrew; Kirby, Evan N.; Hopkins, Philip F.; Ma, Xiangcheng; Wheeler, Coral; Kereš, Dušan; Faucher-Giguère, Claude-André; Quataert, Eliot

2018-02-01

We investigate stellar metallicity distribution functions (MDFs), including Fe and α-element abundances, in dwarf galaxies from the Feedback in Realistic Environment (FIRE) project. We examine both isolated dwarf galaxies and those that are satellites of a Milky Way-mass galaxy. In particular, we study the effects of including a sub-grid turbulent model for the diffusion of metals in gas. Simulations that include diffusion have narrower MDFs and abundance ratio distributions, because diffusion drives individual gas and star particles towards the average metallicity. This effect provides significantly better agreement with observed abundance distributions in dwarf galaxies in the Local Group, including small intrinsic scatter in [α/Fe] versus [Fe/H] of ≲0.1 dex. This small intrinsic scatter arises in our simulations because the interstellar medium in dwarf galaxies is well mixed at nearly all cosmic times, such that stars that form at a given time have similar abundances to ≲0.1 dex. Thus, most of the scatter in abundances at z = 0 arises from redshift evolution and not from instantaneous scatter in the ISM. We find similar MDF widths and intrinsic scatter for satellite and isolated dwarf galaxies, which suggests that environmental effects play a minor role compared with internal chemical evolution in our simulations. Overall, with the inclusion of metal diffusion, our simulations reproduce abundance distribution widths of observed low-mass galaxies, enabling detailed studies of chemical evolution in galaxy formation.

Chemical compatibility study between ceramic breeder and EUROFER97 steel for HCPB-DEMO blanket

Energy Technology Data Exchange (ETDEWEB)

Mukai, Keisuke, E-mail: keisuke.mukai@kit.edu [Institute for Applied Materials (IAM), Karlsruhe Institute of Technology, 76021 Karlsruhe (Germany); Sanchez, Fernando [National Fusion Laboratory, Division of Fusion Technology, CIEMAT, 28040 Madrid (Spain); Knitter, Regina [Institute for Applied Materials (IAM), Karlsruhe Institute of Technology, 76021 Karlsruhe (Germany)

2017-05-15

Chemical compatibility between ceramic breeder (Li{sub 4}SiO{sub 4} + 20 mol% addition of Li{sub 2}TiO{sub 3}) and EUROFER97 steel was examined in this study. These materials were contacted and heated at 623, 823 and 1073 K under He + 0.1 vol.% H{sub 2} atmosphere for up to 12 weeks. Limited influence was found in the breeder specimens, although losses of the constituent elements appeared near the surface of the breeder pellets heated at 1073 K. For the EUROFER specimens with formation of a corrosion layer, element diffusivity was estimated based on diffusion kinetics. In the temperature range, effective diffusion coefficients of oxygen into EUROFER steel were in the range from 3.5 × 10{sup −134} to 2.5 × 10{sup −112} cm/s{sup 2} and found to be faster than that of Li. The coefficients yielded an activation energy of 0.93 eV for oxygen diffusion into EUROFER steel and predicted the possible thickness of the corrosion layer after operational periods.

Oxygen and SO2 Consumption Rates in White and Rosé Wines: Relationship with and Effects on Wine Chemical Composition.

Science.gov (United States)

Carrascón, Vanesa; Bueno, Mónica; Fernandez-Zurbano, Purificación; Ferreira, Vicente

2017-11-01

This Article addresses the study of O 2 and SO 2 consumption rates of white and rosé wines, their relationship to the initial chemical composition, and their effects on the chemical changes experienced by wine during oxidation. Eight wines were subjected to five consecutive air-saturation cycles. O 2 was monitored periodically; SO 2 , color, and antioxidant indexes were determined after each cycle, and the initial and final compositions of the wines were thoroughly determined. Wines consumed oxygen at progressively decreasing rates. In the last cycles, after a strong decrease, consistent increases of oxygen levels were seen. Oxygen consumption rates were satisfactorily modeled, being proportional to wine copper, quercetin, and kaempherol contents and negatively proportional to cinnamic acids. SO 2 consumption rates were highly diverse between wines and were positively related to free SO 2 , Mn, and pH, among others. In the last saturations, SO 2 consumption took place regardless of O 2 consumption, implying that SO 2 should reduce chemical species oxidized in previous saturations. Some volatile phenols seem to be the end point of radical-mediated oxidation of polyphenols taking place preferably in the first saturation.

A quantum-chemical study of oxygen-vacancy defects in PbTiO3 crystals

International Nuclear Information System (INIS)

Stashans, Arvids; Serrano, Sheyla; Medina, Paul

2006-01-01

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO 3 crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results

Twin-domain size and bulk oxygen in-diffusion kinetics of YBa2Cu3O6+x studied by neutron powder diffraction and gas volumetry

DEFF Research Database (Denmark)

Poulsen, H.F.; Andersen, N.H.; Lebech, B.

1991-01-01

which are identified to result from temperature independent twin-domain formation in to different orthorhombic phases with domain sizes 250 and 350 angstrom, respectively. The oxygen in-diffusion flow shows simple relaxation type behaviour J = J0 exp(-t/tau) despite a rather broad particle size...

Quantifying the effect of medium composition on the diffusive mass transfer of hydrophobic organic chemicals through unstirred boundary layers

DEFF Research Database (Denmark)

Mayer, Philipp; Karlson, U.; Christensen, P.S.

2005-01-01

Unstirred boundary layers (UBLs) often act as a bottleneck for the diffusive transport of hydrophobic organic compounds (HOCs) in the environment. Therefore, a microscale technique was developed for quantifying mass transfer through a 100-μm thin UBL, with the medium composition of the UBL...... as the controllable factor. The model compound fluoranthene had to (1) partition from a contaminated silicone disk (source) into the medium, (2) then diffuse through 100 μm of medium (UBL), and finally (3) partition into a clean silicone layer (sink). The diffusive mass transfer from source to sink was monitored over...... of magnitude. These results demonstrate that medium constituents, which normally are believed to bind hydrophobic organic chemicals, actually can enhance the diffusive mass transfer of HOCs in the vicinity of a diffusion source (e.g., contaminated soil particles). The technique can be used to evaluate...

High Selectivity Oxygen Delignification

Energy Technology Data Exchange (ETDEWEB)

Lucian A. Lucia

2005-11-15

Project Objective: The objectives of this project are as follows: (1) Examine the physical and chemical characteristics of a partner mill pre- and post-oxygen delignified pulp and compare them to lab generated oxygen delignified pulps; (2) Apply the chemical selectivity enhancement system to the partner pre-oxygen delignified pulps under mill conditions (with and without any predetermined amounts of carryover) to determine how efficiently viscosity is preserved, how well selectivity is enhanced, if strength is improved, measure any yield differences and/or bleachability differences; and (3) Initiate a mill scale oxygen delignification run using the selectivity enhancement agent, collect the mill data, analyze it, and propose any future plans for implementation.

Efficacy and safety of a new superficial chemical peel using alpha-hydroxy acid, vitamin C and oxygen for melasma.

Science.gov (United States)

Kim, Won-Serk

2013-02-01

Facial skin pigmentary disorders can be resistant to conventional treatment. Superficial chemical peel is an effective and safe treatment in pigmentary problems including melasma, post-inflammatory hyperpigmentation and aging spots. To assess the efficacy and safety of new superficial chemical peel (Melasma peel, Theraderm®), this is composed of alpha-hydroxy acid (AHAs), vitamin C and oxygen for melasma. Twenty-five ethnic Korean patients (Fitzpatrick skin phototypes IV and V) with moderate to severe melasma were enrolled. The patients underwent four treatments at 1-2-week intervals for 8 weeks. Clinical improvement was evaluated on a 5-point scale by participants and by the same dermatologist, and adverse effects were checked during the study. Improvement in the degree of pigmentation, pores, and evenness were noted. Significant clinical improvement of hyperpigmentation was evident. No adverse effects were reported. New superficial chemical peel using AHAs, vitamin C and oxygen is an effective and very safe treatment for melasma.

Active packaged lamb with oxygen scavenger/carbon dioxide emitter sachet: physical-chemical and microbiological stability during refrigerated storage

Directory of Open Access Journals (Sweden)

Marco Antonio Trindade

2013-09-01

Full Text Available Lamb meat has been commercialized in Brazil almost exclusively as a frozen product due to the longer shelf life provided by freezing when compared to refrigeration. However, as a result of the current trend of increased demand for convenience products, a need has emerged for further studies to facilitate the marketing of refrigerated lamb cuts. The aim of the present study was to evaluate the contribution of active packaging technology in extending the shelf life of lamb loins (Longissimus lumborum stored under refrigeration (1±1 ° C when compared to the traditional vacuum packaging. For this purpose, two kinds of sachets were employed: oxygen scavenger sachet and oxygen scavenger/carbon dioxide emitter sachet. Experiments were conducted in three treatments: 1 Vacuum (Control, 2 Vacuum + oxygen scavenger sachet and 3 Vacuum + oxygen scavenger/carbon dioxide emitter sachet. Microbiological (counts of anaerobic psychrotrophs, coliform at 45 ° C, coagulase-positive staphylococci, Salmonella and lactic acid bacteria and physical-chemical (thiobarbituric acid reactive substances, objective color, pH value, water loss from cooking and shear force analyses were carried out weekly for a total storage period of 28 days. The experiment was performed three times for all treatments. Results showed that the lamb meat remained stable with respect to the majority of the evaluated physical and chemical indexes and remained within the standards established by Brazilian legislation for pathogenic microorganisms throughout the storage period in all three packaging systems. However, all treatments presented elevated counts of anaerobic psychrotrophic microorganisms and lactic acid bacteria, reaching values above 10(7 CFU/g at 28 days of storage. Thus, under the conditions tested, neither the oxygen scavenger sachet nor the dual function sachet (oxygen scavenger/carbon dioxide emitter were able to extend the shelf life of refrigerated lamb loin when added to this

A combined kinetic and diffusion model for pyrite oxidation in tailings - a change in controls with time

International Nuclear Information System (INIS)

Elberling, B.; Nicholson, R.V.; Scharer, J.M.

1994-01-01

Acidic drainage from the oxidation of mine tailing wastes is an important environmental problem. The purpose of this paper is to develop a model (1) to simulate the rate of oxidation of pyrite over time, (2) to verify the importance of chemical kinetic control and diffusion control on the oxidation rate with time and, (3) to evaluate the sensitivity of the model to critical parameters of the tailings, such as grain size, pyrite content and the effective diffusion coefficient. The source code comprises four main modules including parameter allocation (kinetics, transport), sulphide oxidation (shrinking particle), oxygen transport and pyrite mass balance. The results show that high oxidation rates are observed in the initial time after tailings deposition. During this initial period of high rates, an apparent shift occurs from kinetic to diffusional control over a period of time that depends on the composition and properties of the tailings. Based on the simulation results, it is evident that the overall rate of oxidation after a few years will be controlled dominantly by the diffusion of oxygen rather than by biological or non-biological kinetics in the tailings

Suppression of oxygen diffusion by thin Al2O3 films grown on SrTiO3 studied using a monoenergetic positron beam

International Nuclear Information System (INIS)

Uedono, A.; Kiyohara, M.; Yasui, N.; Yamabe, K.

2005-01-01

The annealing behaviors of oxygen vacancies introduced by the epitaxial growth of thin SrTiO 3 and Al 2 O 3 films on SrTiO 3 substrates were studied by using a monoenergetic positron beam. The films were grown by molecular-beam epitaxy without using an oxidant. The Doppler broadening spectra of the annihilation radiation were measured as a function of the incident positron energy for samples fabricated under various growth conditions. The line-shape parameter S, corresponding to the annihilation of positrons in the substrate, was increased by the film growth, suggesting diffusion of oxygen from the substrate into the film and a resultant introduction of vacancies (mainly oxygen vacancies). A clear correlation between the value of S and the substrate conductivity was obtained. From isochronal annealing experiments, the Al 2 O 3 thin film was found to suppress the penetration of oxygen from the atmosphere for annealing temperatures below 600 deg. C. Degradation of the film's oxygen blocking property occurred due to the annealing at 700 deg. C, and this was attributed to the oxidation of the Al 2 O 3 by the atmosphere and the resultant introduction of vacancy-type defects

Oxygenated hemoglobin diffuse reflectance ratio for in vitro detection of human gastric pre-cancer

Science.gov (United States)

Li, L. Q.; Wei, H. J.; Guo, Z. Y.; Yang, H. Q.; Wu, G. Y.; Xie, S. S.; Zhong, H. Q.; Li, X. Y.; Zhao, Q. L.; Guo, X.

2010-07-01

Oxygenated hemoglobin diffuse reflectance (DR) ratio (R540/R575) method based on DR spectral signatures is used for early diagnosis of malignant lesions of human gastric epithelial tissues in vitro. The DR spectra for four different kinds of gastric epithelial tissues were measured using a spectrometer with an integrating sphere detector in the spectral range from 400 to 650 nm. The results of measurement showed that the average DR spectral intensity for the epithelial tissues of normal stomach is higher than that for the epithelial tissues of chronic and malignant stomach and that for the epithelial tissues of chronic gastric ulcer is higher than that for the epithelial tissues of malignant stomach. The average DR spectra for four different kinds of gastric epithelial tissues show dips at 542 and 577 nm owing to absorption from oxygenated Hemoglobin (HbO2). The differences in the mean R540/R575 ratios of HbO2 bands are 6.84% between the epithelial tissues of normal stomach and chronic gastric ulcer, 14.7% between the epithelial tissues of normal stomach and poorly differentiated gastric adenocarcinoma and 22.6% between the epithelial tissues of normal stomach and undifferentiated gastric adenocarcinoma. It is evident from results that there were significant differences in the mean R540/R575 ratios of HbO2 bands for four different kinds of gastric epithelial tissues in vitro ( P < 0.01).

Incorporation, diffusion and segregation of impurities in polycrystalline silicon

Energy Technology Data Exchange (ETDEWEB)

Deville, J.P.; Soltani, M.L. (Universite Louis Pasteur, 67 - Strasbourg (France)); Quesada, J. (Laboratoire de Metallurgie-Chimie des Materiaux, E.N.S.A.I.S., 67 - Strasbourg (France))

1982-01-01

We studied by means of X-Ray photoelectron Spectroscopy the nature, distribution and, when possible, the chemical bond of impurities at the surface of polycrystalline silicon samples grown on a carbon ribbon. Besides main impurities (carbon and oxygen), always present at concentrations around their limit of solubility in silicon, metal impurities have been found: their nature varies from one sample to another. Their spatial distribution is not random: some are strictly confined at the surface (sodium), whereas others are in the superficial oxidized layer (calcium, magnesium) or localized at the oxide-bulk silicon interface (iron). Metal impurities are coming from the carbon ribbon and are incorporated to silicon during the growth process. It is not yet possible to give a model of diffusion processes of impurities since they are too numerous and interact one with the other. However oxygen seems to play a leading role in the spatial distribution of metal impurities.

Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium-Oxygen Batteries.

Science.gov (United States)

Wang, Wanwan; Lai, Nien-Chu; Liang, Zhuojian; Wang, Yu; Lu, Yi-Chun

2018-04-23

Rechargeable potassium-oxygen (K-O 2 ) batteries promise to provide higher round-trip efficiency and cycle life than other alkali-oxygen batteries with satisfactory gravimetric energy density (935 Wh kg -1 ). Exploiting a strong electron-donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO 2 ), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO-based K-O 2 battery demonstrates a much higher energy efficiency and stability than the glyme-based electrolyte. A universal KO 2 growth model is developed and it is demonstrated that the ideal solvent for K-O 2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen enriched air using membrane for palm oil wastewater treatment

Directory of Open Access Journals (Sweden)

Ramlah Mohd Tajuddin

2002-11-01

Full Text Available A research aimed to explore new method of aeration using oxygen enriched air performance on BOD reduction of palm oil wastewater was conducted. The oxygen enriched air was obtained from an Oxygen Enriched System (OES developed using asymmetric polysulfone hollow fiber membrane with composition consisting of PSF: 22%, DMAc: 31.8%, THF: 31.8%, EtOH: 14.4%. Palm oil wastewater samples were taken from facultative pond effluent. These samples were tested for its initial biochemical oxygen demand (BOD, total suspended solids (TSS, pH, conductivity, turbidity, dissolved oxygen (DO, suspended solids (SS, and total dissolved solids (TDS before being subjected to two modes of aeration system, that is diffused air and oxygen enriched air. These water quality concentrations were tested for every 20 minutes for two-hour period during the aeration process. Results of BOD, TSS, pH, conductivity, DO, SS and TDS concentrations against time of samples from the two modes of aeration were then compared. It was found that DO concentration achieved in oxygen enriched air aeration was better than aeration using diffused air system. Aeration using OES improve the DO concentration in the wastewater and thus improve the BOD reduction and also influence other physical characteristics of wastewater. This phenomenon indicates the advantage of using air with higher oxygen concentration for wastewater aeration instead of diffused air system.

Effects of normobaric versus hyperbaric oxygen on cell injury induced by oxygen and glucose deprivation in acute brain slices

OpenAIRE

Laurent Chazalviel; Jean-Eric Blatteau; Nicolas Vallée; Jean-Jacques Risso; Stéphane Besnard; Jacques H Abraini

2016-01-01

Normobaric oxygen (NBO) and hyperbaric oxygen (HBO) are emerging as a possible co-treatment of acute ischemic stroke. Both have been shown to reduce infarct volume, to improve neurologic outcome, to promote endogenous tissue plasminogen activator-induced thrombolysis and cerebral blood flow, and to improve tissue oxygenation through oxygen diffusion in the ischemic areas, thereby questioning the interest of HBO compared to NBO. In the present study, in order to investigate and compare the oxy...

Enhanced oxygen diffusion in low barium-containing La0.2175Pr0.2175Ba0.145Sr0.4Fe0.8Co0.2O3−δ intermediate temperature solid oxide fuel cell cathodes

KAUST Repository

Vert, Vicente B.

2012-09-01

Isotopic tracer diffusion studies have been performed on the perovskite composition La 0.2175Pr 0.2175Ba 0.145Sr 0.4Fe 0.8Co 0.2O 3-δ to obtain the diffusion and surface exchange coefficients for oxygen. This material has been identified as a highly active electrocatalytic cathode for intermediate temperature solid oxide fuel cells. The oxygen diffusion coefficients obtained in the 450-650 °C temperature range are higher than the ones measured for most of the cathode materials reported in the literature and they agree with those calculated from electrochemical impedance spectroscopy measurements performed on symmetrical cells. © 2012 Elsevier B.V. All rights reserved.

Thermal and mechanical behaviour of oxygen carrier materials for chemical looping combustion in a packed bed reactor

NARCIS (Netherlands)

Jacobs, M.; Van Noyen, J.; Larring, Y.; McCann, M.; Pishahang, M.; Amini, S.; Ortiz, M.; Galluci, F.; Sint-Annaland, M. V.; Tournigant, D.; Louradour, E.; Snijkers, F.

2015-01-01

Chemical looping combustion (CLC) is a promising carbon capture technology where cyclic reduction and oxidation of a metallic oxide, which acts as a solid oxygen carrier, takes place. With this system, direct contact between air and fuel can be avoided, and so, a concentrated CO2 stream is generated

A theoretical evaluation of the oxygen concentration in a corrosion-fatigue crack

International Nuclear Information System (INIS)

Turnbull, A.

1981-01-01

The oxygen concentration in a corrosion-fatigue crack has been evaluated theoretically by assuming that oxygen was consumed by cathodic reduction on the walls of the crack and mass transport occurred by diffusion and advection (forced convection), with the latter resulting from the sinusoidal variation of the displacement of the crack walls. By using parameters relevant to a compact tension specimen, the time-dependent distribution of the oxygen concentration in the crack was calculated as a function of ΔK (the range of the stress intensity factor), R-value (minimum load/maximum load), frequency, crack length, and electrode potential. The influence of advection was to significantly enhance the mass transport of oxygen in the crack compared with ''diffusion-only'' even at low frequencies and low ΔK. Regions in the crack were identified in which advection dominance or diffusion dominance of the mass transport of oxygen occurred

Diffuse reflectance spectroscopy for the measurement of tissue oxygen saturation

International Nuclear Information System (INIS)

Sircan-Kucuksayan, A; Canpolat, M; Uyuklu, M

2015-01-01

Tissue oxygen saturation (StO 2 ) is a useful parameter for medical applications. A spectroscopic method has been developed to detect pathologic tissues, due to a lack of normal blood circulation, by measuring StO 2 . In this study, human blood samples with different levels of oxygen saturation have been prepared and spectra were acquired using an optical fiber probe to investigate the correlation between the oxygen saturation levels and the spectra. A linear correlation between the oxygen saturation and ratio of the intensities (760 nm to 790 nm) of the spectra acquired from blood samples has been found. In a validation study, oxygen saturations of the blood samples were estimated from the spectroscopic measurements with an error of 2.9%. It has also been shown that the linear dependence between the ratio and the oxygen saturation of the blood samples was valid for the blood samples with different hematocrits. Spectra were acquired from the forearms of 30 healthy volunteers to estimate StO 2 prior to, at the beginning of, after 2 min, and at the release of total vascular occlusion. The average StO 2 of a forearm before and after the two minutes occlusion was significantly different. The results suggested that optical reflectance spectroscopy is a sensitive method to estimate the StO 2 levels of human tissue. The technique developed to measure StO 2 has potential to detect ischemia in real time. (paper)

Determination of Krypton Diffusion Coefficients in Uranium Dioxide Using Atomic Scale Calculations.

Science.gov (United States)

Vathonne, Emerson; Andersson, David A; Freyss, Michel; Perriot, Romain; Cooper, Michael W D; Stanek, Christopher R; Bertolus, Marjorie

2017-01-03

We present a study of the diffusion of krypton in UO 2 using atomic scale calculations combined with diffusion models adapted to the system studied. The migration barriers of the elementary mechanisms for interstitial or vacancy assisted migration are calculated in the DFT+U framework using the nudged elastic band method. The attempt frequencies are obtained from the phonon modes of the defect at the initial and saddle points using empirical potential methods. The diffusion coefficients of Kr in UO 2 are then calculated by combining this data with diffusion models accounting for the concentration of vacancies and the interaction of vacancies with Kr atoms. We determined the preferred mechanism for Kr migration and the corresponding diffusion coefficient as a function of the oxygen chemical potential μ O or nonstoichiometry. For very hypostoichiometric (or U-rich) conditions, the most favorable mechanism is interstitial migration. For hypostoichiometric UO 2 , migration is assisted by the bound Schottky defect and the charged uranium vacancy, V U 4- . Around stoichiometry, migration assisted by the charged uranium-oxygen divacancy (V UO 2- ) and V U 4- is the favored mechanism. Finally, for hyperstoichiometric or O-rich conditions, the migration assisted by two V U 4- dominates. Kr migration is enhanced at higher μ O , and in this regime, the activation energy will be between 4.09 and 0.73 eV depending on nonstoichiometry. The experimental values available are in the latter interval. Since it is very probable that these values were obtained for at least slightly hyperstoichiometric samples, our activation energies are consistent with the experimental data, even if further experiments with precisely controlled stoichiometry are needed to confirm these results. The mechanisms and trends with nonstoichiometry established for Kr are similar to those found in previous studies of Xe.

OXYGEN DEPLETION IN THE INTERSTELLAR MEDIUM: IMPLICATIONS FOR GRAIN MODELS AND THE DISTRIBUTION OF ELEMENTAL OXYGEN

International Nuclear Information System (INIS)

Whittet, D. C. B.

2010-01-01

This paper assesses the implications of a recent discovery that atomic oxygen is being depleted from diffuse interstellar gas at a rate that cannot be accounted for by its presence in silicate and metallic oxide particles. To place this discovery in context, the uptake of elemental O into dust is considered over a wide range of environments, from the tenuous intercloud gas and diffuse clouds sampled by the depletion observations to dense clouds where ice mantles and gaseous CO become important reservoirs of O. The distribution of O in these contrasting regions is quantified in terms of a common parameter, the mean number density of hydrogen (n H ). At the interface between diffuse and dense phases (just before the onset of ice-mantle growth) as much as ∼160 ppm of the O abundance is unaccounted for. If this reservoir of depleted oxygen persists to higher densities it has implications for the oxygen budget in molecular clouds, where a shortfall of the same order is observed. Of various potential carriers, the most plausible appears to be a form of O-bearing carbonaceous matter similar to the organics found in cometary particles returned by the Stardust mission. The 'organic refractory' model for interstellar dust is re-examined in the light of these findings, and it is concluded that further observations and laboratory work are needed to determine whether this class of material is present in quantities sufficient to account for a significant fraction of the unidentified depleted oxygen.

Oxygen permeation in thin, dense Ce0.9Gd0.1O 1.95- membranes I. Model study

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos; Søgaard, Martin; Hendriksen, Peter Vang

2011-01-01

at the feed and permeate side of the membrane, related to the gaseous oxygen reduction and fuel oxidation, respectively, as well as the gas conversion and gas diffusion resistances in the porous support structure at the permeate side. The temperature and oxygen activity dependence of the oxide ionic...... was analyzed by a separation of the various losses. The chemical expansion of Ce 0.9Gd0.1O1.95-δ under operation was estimated from the calculated oxygen activity and nonstoichiometry profiles inside the membrane. © 2011 The Electrochemical Society.......A model of a supported planar Ce0.9Gd0.1O 1.95-δ oxygen membrane in a plug-flow setup was constructed and a sensitivity analysis of its performance under varying operating conditions and membrane parameters was performed. The model takes into account the driving force losses at the catalysts...

Modeling and control of diffusion and low-pressure chemical vapor deposition furnaces

Science.gov (United States)

De Waard, H.; De Koning, W. L.

1990-03-01

In this paper a study is made of the heat transfer inside cylindrical resistance diffusion and low-pressure chemical vapor deposition furnaces, aimed at developing an improved temperature controller. A model of the thermal behavior is derived which also covers the important class of furnaces equipped with semitransparent quartz process tubes. The model takes into account the thermal behavior of the thermocouples. It is shown that currently used temperature controllers are highly inefficient for very large scale integration applications. Based on the model an alternative temperature controller of the linear-quadratic-Gaussian type is proposed which features direct wafer temperature control. Some simulation results are given.

Substitution and diffusion of Cr 2+ and Cr 3+ in synthetic forsterite and natural olivine at 1200–1500 °C and 1 bar

Energy Technology Data Exchange (ETDEWEB)

Jollands, M. C.; O' Neill, H. St. C.; Van Orman, J.; Berry, A. J.; Hermann, J.; Newville, M.; Lanzirotti, A.

2018-01-01

The diffusion and substitution mechanisms of Cr in forsterite were studied as a function of crystallographic orientation and the chemical potentials of all four components in the system MgO-SiO2-Cr-O. Oxygen fugacity (fO2) was varied over 15.4 log units at 1400 °C and was fixed at the iron-wüstite equilibrium for a temperature series (1200–1500 °C). The valence state changes of Cr along some diffusion profiles was also investigated using X-ray absorption near edge structure spectroscopy.

High temperature properties of Zircaloy--oxygen alloys

International Nuclear Information System (INIS)

Mellinger, G.B.; Bates, J.L.

1977-03-01

The effect of oxygen on three properties of Zircaloy-4 cladding relevant to LOCA evaluation codes was determined. Thermal expansion, elastic moduli, and thermal diffusivity were measured over the range room temperature--1200 0 C (2192 0 F) and 0.7 to 28 at.% oxygen. Thermal expansion and elastic moduli showed increases with oxygen concentration, while thermal diffusivity tended to decrease. Zircaloy-2 was examined over the same temperature range, but only to 5 at.% oxygen, differences in the properties between the two alloys were minor. The thermal emittance of Zircaloy-4 was measured in argon over the wavelength range 1.5 to 2.5 μm on previously oxidized tubing and on surfaces in the process of oxidizing in unlimited steam. For the latter, a high emittance (approximately 0.9) was reached at an oxide thickness of about 100 mg/dm 2 , and the tubing surface remained black and substoichiometric as oxidation continued at temperatures to 1200 0 C

Mathematical aspects of reacting and diffusing systems

CERN Document Server

Fife, Paul C

1979-01-01

Modeling and analyzing the dynamics of chemical mixtures by means of differ- tial equations is one of the prime concerns of chemical engineering theorists. These equations often take the form of systems of nonlinear parabolic partial d- ferential equations, or reaction-diffusion equations, when there is diffusion of chemical substances involved. A good overview of this endeavor can be had by re- ing the two volumes by R. Aris (1975), who himself was one of the main contributors to the theory. Enthusiasm for the models developed has been shared by parts of the mathematical community, and these models have, in fact, provided motivation for some beautiful mathematical results. There are analogies between chemical reactors and certain biological systems. One such analogy is rather obvious: a single living organism is a dynamic structure built of molecules and ions, many of which react and diffuse. Other analogies are less obvious; for example, the electric potential of a membrane can diffuse like a chemical, and ...

Modelling chemical reactions in dc plasma inside oxygen bubbles in water

International Nuclear Information System (INIS)

Takeuchi, N; Ishii, Y; Yasuoka, K

2012-01-01

Plasmas generated inside oxygen bubbles in water have been developed for water purification. Zero-dimensional numerical simulations were used to investigate the chemical reactions in plasmas driven by dc voltage. The numerical and experimental results of the concentrations of hydrogen peroxide and ozone in the solution were compared with a discharge current between 1 and 7 mA. Upon increasing the water vapour concentration inside bubbles, we saw from the numerical results that the concentration of hydrogen peroxide increased with discharge current, whereas the concentration of ozone decreased. This finding agreed with the experimental results. With an increase in the discharge current, the heat flux from the plasma to the solution increased, and a large amount of water was probably vaporized into the bubbles.

Modelling chemical reactions in dc plasma inside oxygen bubbles in water

Science.gov (United States)

Takeuchi, N.; Ishii, Y.; Yasuoka, K.

2012-02-01

Plasmas generated inside oxygen bubbles in water have been developed for water purification. Zero-dimensional numerical simulations were used to investigate the chemical reactions in plasmas driven by dc voltage. The numerical and experimental results of the concentrations of hydrogen peroxide and ozone in the solution were compared with a discharge current between 1 and 7 mA. Upon increasing the water vapour concentration inside bubbles, we saw from the numerical results that the concentration of hydrogen peroxide increased with discharge current, whereas the concentration of ozone decreased. This finding agreed with the experimental results. With an increase in the discharge current, the heat flux from the plasma to the solution increased, and a large amount of water was probably vaporized into the bubbles.

Molecular Diffusion Coefficients: Experimental Determination and Demonstration.

Science.gov (United States)

Fate, Gwendolyn; Lynn, David G.

1990-01-01

Presented are laboratory methods which allow the demonstration and determination of the diffusion coefficients of compounds ranging in size from water to small proteins. Included are the procedures involving the use of a spectrometer, UV cell, triterated agar, and oxygen diffusion. Results including quantification are described. (CW)

A comparison of measured radionuclide release rates from Three Mile Island Unit-2 core debris for different oxygen chemical potentials

International Nuclear Information System (INIS)

Baston, V.F.; Hofstetter, K.J.; Ryan, R.F.

1987-01-01

Chemical and radiochemical analyses of reactor coolant samples taken during defueling of the Three Mile Island Unit-2 (TMI-2) reactor provide relevant data to assist in understanding the solution chemistry of the radionuclides retained within the TMI-2 reactor coolant system. Hydrogen peroxide was added to various plant systems to provide disinfection for microbial contamination and has provided the opportunity to observe radionuclide release under different oxygen chemical potentials. A comparison of the radionuclide release rates with and without hydrogen peroxide has been made for these separate but related cases, i.e., the fuel transfer canal and connecting spent-fuel pool A with the TMI-2 reactor plenum in the fuel transfer canal, core debris grab sample laboratory experiments, and the reactor vessel fluid and associated core debris. Correlation and comparison of these data indicate a physical parameter dependence (surface-to-volume ratio) affecting all radionuclide release; however, selected radionuclides also demonstrate a chemical dependence release under the different oxygen chemical potentials. Chemical and radiochemical analyses of reactor coolant samples taken during defueling of the Three Mile Island Unit-2 (TMI-2) reactor provide relevant data to assist in understanding the solution chemistry of the radionuclides retained within the TMI-2 reactor coolant system

EVOLUTION OF WHITE DWARF STARS WITH HIGH-METALLICITY PROGENITORS: THE ROLE OF 22Ne DIFFUSION

International Nuclear Information System (INIS)

Althaus, L. G.; Corsico, A. H.; GarcIa-Berro, E.; Renedo, I.; Isern, J.; Rohrmann, R. D.

2010-01-01

Motivated by the strong discrepancy between the main-sequence turnoff age and the white dwarf cooling age in the metal-rich open cluster NGC 6791, we compute a grid of white dwarf evolutionary sequences that incorporates for the first time the energy released by the processes of 22 Ne sedimentation and of carbon/oxygen phase separation upon crystallization. The grid covers the mass range from 0.52 to 1.0 M sun , and is appropriate for the study of white dwarfs in metal-rich clusters. The evolutionary calculations are based on a detailed and self-consistent treatment of the energy released from these two processes, as well as on the employment of realistic carbon/oxygen profiles, of relevance for an accurate evaluation of the energy released by carbon/oxygen phase separation. We find that 22 Ne sedimentation strongly delays the cooling rate of white dwarfs stemming from progenitors with high metallicities at moderate luminosities, while carbon/oxygen phase separation adds considerable delays at low luminosities. Cooling times are sensitive to possible uncertainties in the actual value of the diffusion coefficient of 22 Ne. Changing the diffusion coefficient by a factor of 2 leads to maximum age differences of ∼8%-20% depending on the stellar mass. We find that the magnitude of the delays resulting from chemical changes in the core is consistent with the slowdown in the white dwarf cooling rate that is required to solve the age discrepancy in NGC 6791.

No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

Science.gov (United States)

Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming

2012-10-01

In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for

Diffusion and crystal growth in plasma deposed thin ITO films

International Nuclear Information System (INIS)

Steffen, H.; Wulff, H.; Quaas, M.; Tun, Tin Maung.; Hipple, R.

2000-01-01

Tin-doped indium oxide (ITO) films were deposited by means of DC-planar magnetron sputtering. A metallic In/Sn (90/10) target an Ar/O 2 gas mixture were used. The oxygen flow was varied between 0 and 2 sccm. Substrate voltages between 0 and -100 V were used. With increasing oxygen flow film structure and composition change from crystalline metallic In/Sn to amorphous ITO. Simultaneously the deposition rate decreases and the film density increases. The diffusion of oxygen into metallic In/Sn films and the amorphous-to-crystalline transformation of ITO were studied using in situ grazing incidence X-ray diffractometry (GIXRD), grazing incidence reflectometry (GIXR), and AFM. From the X-ray integral intensities diffusion constants, activation energies of the diffusion, reaction order and activation energy of the crystal growth were extracted. (authors)

Study of the decarburization of 18-8 stainless steel by oxygen at low pressure

International Nuclear Information System (INIS)

Armand, G.; Lapujoulade, J.

1964-01-01

The kinetic of the decarburization of a 18-8 stainless-steel by oxygen at low pressure has been studied between 1050 and 1200 C. The measurement of the carbon content of the sample is carried out by chemical analysis. Three mechanisms take place in that decarburization: diffusion of carbon in the steel; velocity at the superficial reaction C + 1/2 O 2 ↔ CO; pumping out of CO. The second mechanism seems to govern the overall kinetic. The activation energy of the phenomenon is 108 ± 24 Kcal/mole. (authors) [fr

Insights into thermal diffusion of germanium and oxygen atoms in HfO{sub 2}/GeO{sub 2}/Ge gate stacks and their suppressed reaction with atomically thin AlO{sub x} interlayers

Energy Technology Data Exchange (ETDEWEB)

Ogawa, Shingo, E-mail: Shingo-Ogawa@trc.toray.co.jp [Toray Research Center, Inc., 3-3-7 Sonoyama, Otsu, Shiga 520-8567 (Japan); Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Asahara, Ryohei; Minoura, Yuya; Hosoi, Takuji, E-mail: hosoi@mls.eng.osaka-u.ac.jp; Shimura, Takayoshi; Watanabe, Heiji [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Sako, Hideki; Kawasaki, Naohiko; Yamada, Ichiko; Miyamoto, Takashi [Toray Research Center, Inc., 3-3-7 Sonoyama, Otsu, Shiga 520-8567 (Japan)

2015-12-21

The thermal diffusion of germanium and oxygen atoms in HfO{sub 2}/GeO{sub 2}/Ge gate stacks was comprehensively evaluated by x-ray photoelectron spectroscopy and secondary ion mass spectrometry combined with an isotopic labeling technique. It was found that {sup 18}O-tracers composing the GeO{sub 2} underlayers diffuse within the HfO{sub 2} overlayers based on Fick's law with the low activation energy of about 0.5 eV. Although out-diffusion of the germanium atoms through HfO{sub 2} also proceeded at the low temperatures of around 200 °C, the diffusing germanium atoms preferentially segregated on the HfO{sub 2} surfaces, and the reaction was further enhanced at high temperatures with the assistance of GeO desorption. A technique to insert atomically thin AlO{sub x} interlayers between the HfO{sub 2} and GeO{sub 2} layers was proven to effectively suppress both of these independent germanium and oxygen intermixing reactions in the gate stacks.

Impact of Dissolved Oxygen during UV-Irradiation on the Chemical Composition and Function of CHO Cell Culture Media.

Science.gov (United States)

Meunier, Sarah M; Todorovic, Biljana; Dare, Emma V; Begum, Afroza; Guillemette, Simon; Wenger, Andrew; Saxena, Priyanka; Campbell, J Larry; Sasges, Michael; Aucoin, Marc G

2016-01-01

Ultraviolet (UV) irradiation is advantageous as a sterilization technique in the biopharmaceutical industry since it is capable of targeting non-enveloped viruses that are typically challenging to destroy, as well as smaller viruses that can be difficult to remove via conventional separation techniques. In this work, we investigated the influence of oxygen in the media during UV irradiation and characterized the effect on chemical composition using NMR and LC-MS, as well as the ability of the irradiated media to support cell culture. Chemically defined Chinese hamster ovary cell growth media was irradiated at high fluences in a continuous-flow UV reactor. UV-irradiation caused the depletion of pyridoxamine, pyridoxine, pyruvate, riboflavin, tryptophan, and tyrosine; and accumulation of acetate, formate, kynurenine, lumichrome, and sarcosine. Pyridoxamine was the only compound to undergo complete degradation within the fluences considered; complete depletion of pyridoxamine was observed at 200 mJ/cm2. Although in both oxygen- and nitrogen-saturated media, the cell culture performance was affected at fluences above 200 mJ/cm2, there was less of an impact on cell culture performance in the nitrogen-saturated media. Based on these results, minimization of oxygen in cell culture media prior to UV treatment is recommended to minimize the negative impact on sensitive media.

Combination of chemical suppression techniques for dual suppression of fat and silicone at diffusion-weighted MR imaging in women with breast implants

Energy Technology Data Exchange (ETDEWEB)

Koh, Dow-Mu; Hughes, J. [Royal Marsden Hospital, Department of Radiology, Sutton (United Kingdom); Blackledge, M.; Leach, M.O.; Collins, D.J. [Institute of Cancer Research, CR UK-EPSRC Cancer Imaging Centre, Sutton (United Kingdom); Burns, S. [Nuada 3T MRI Centre, London (United Kingdom); Stemmer, A.; Kiefer, B. [Siemens Healthcare, Erlangen (Germany)

2012-12-15

Silicone breast prostheses prove technically challenging when performing diffusion-weighted MR imaging in the breasts. We describe a combined fat and chemical suppression scheme to achieve dual suppression of fat and silicone, thereby improving the quality of diffusion-weighted images in women with breast implants. MR imaging was performed at 3.0 and 1.5 T in women with silicone breast implants using short-tau inversion recovery (STIR) fat-suppressed echo-planar (EPI) diffusion-weighted MR imaging (DWI) on its own and combined with the slice-select gradient-reversal (SSGR) technique. Imaging was performed using dedicated breast imaging coils. Complete suppression of the fat and silicone signal was possible at 3.0 T using EPI DWI with STIR and SSGR, evaluated with dedicated breast coils. However, a residual silicone signal was still perceptible at 1.5 T using this combined approach. Nevertheless, a further reduction in silicone signal at 1.5 T could be achieved by employing thinner slice partitions and the addition of the chemical-selective fat-suppression (CHESS) technique. DWI using combined STIR and SSGR chemical suppression techniques is feasible to eliminate or reduce silicone signal from prosthetic breast implants. (orig.)

The fate of sulphur in the Cu-based Chemical Looping with Oxygen Uncoupling (CLOU) Process

International Nuclear Information System (INIS)

Adánez-Rubio, Iñaki; Abad, Alberto; Gayán, Pilar; García-Labiano, Francisco; Diego, Luis F. de; Adánez, Juan

2014-01-01

Highlights: • 15 h of CLOU experiments using lignite were carried out in a continuously unit. • The sulphur split between fuel- and air-reactor streams in the process was analysed. • Most of the sulphur introduced with the fuel exits as SO 2 at the fuel-reactor. • The use of a carbon separation system to reduce the S emission was evaluated. • Coals with high S content can be burnt in a CLOU process with a Cu-based material. - Abstract: The Chemical Looping with Oxygen Uncoupling (CLOU) process is a type of Chemical Looping Combustion (CLC) technology that allows the combustion of solid fuels with air, as with conventional combustion, through the use of oxygen carriers that release gaseous oxygen inside the fuel reactor. The aim of this work was to study the behaviour of the sulphur present in fuel during CLOU combustion. Experiments using lignite as fuel were carried out in a continuously operated 1.5 kW th CLOU unit during more than 15 h. Particles containing 60 wt.% CuO on MgAl 2 O 4 , prepared by spray drying, were used as the oxygen carrier in the CLOU process. The temperature in the fuel reactor varied between 900 and 935 °C. CO 2 capture, combustion efficiency and the sulphur split between fuel and air reactor streams in the process were analysed. Complete combustion of the fuel to CO 2 and H 2 O was found in all experiments. Most of the sulphur introduced with the fuel exited as SO 2 at the fuel reactor outlet, although a small amount of SO 2 was measured at the air reactor outlet. The SO 2 concentration in the air reactor exit flow decreased as the temperature in the fuel reactor increased. A carbon capture efficiency of 97.6% was achieved at 935 °C, with 87.9 wt.% of the total sulphur exiting as SO 2 in the fuel reactor. Both the reactivity and oxygen transport capacity of the oxygen carrier were unaffected during operation with a high sulphur content fuel, and agglomeration problems did not occur. Predictions were calculated regarding the use

Analytical model of chemical phase and formation of DSB in chromosomes by ionizing radiation.

Science.gov (United States)

Barilla, Jiří; Lokajíček, Miloš; Pisaková, Hana; Simr, Pavel

2013-03-01

Mathematical analytical model of the processes running in individual radical clusters during the chemical phase (under the presence of radiomodifiers) proposed by us earlier has been further developed and improved. It has been applied to the data presented by Blok and Loman characterizing the oxygen effect in SSB and DSB formation (in water solution and at low-LET radiation) also in the region of very small oxygen concentrations, which cannot be studied with the help of experiments done with living cells. In this new analysis the values of all reaction rates and diffusion parameters known from literature have been made use of. The great increase of SSB and DSB at zero oxygen concentration may follow from the fact that at small oxygen concentrations the oxygen absorbs other radicals while at higher concentrations the formation of oxygen radicals prevails. It explains the double oxygen effect found already earlier by Ewing. The model may be easily extended to include also the effects of other radiomodifiers present in medium during irradiation.

Analytical model of chemical phase and formation of DSB in chromosomes by ionizing radiation

International Nuclear Information System (INIS)

Barilla, Jiři; Simr, Pavel; Lokajíček, Miloš; Pisaková, Hana

2013-01-01

Mathematical analytical model of the processes running in individual radical clusters during the chemical phase (under the presence of radiomodifiers) proposed by us earlier has been further developed and improved. It has been applied to the data presented by Blok and Loman characterizing the oxygen effect in SSB and DSB formation (in water solution and at low-LET radiation) also in the region of very small oxygen concentrations, which cannot be studied with the help of experiments done with living cells. In this new analysis the values of all reaction rates and diffusion parameters known from literature have been made use of. The great increase of SSB and DSB at zero oxygen concentration may follow from the fact that at small oxygen concentrations the oxygen absorbs other radicals while at higher concentrations the formation of oxygen radicals prevails. It explains the double oxygen effect found already earlier by Ewing. The model may be easily extended to include also the effects of other radiomodifiers present in medium during irradiation.

A quantum-chemical study of oxygen-vacancy defects in PbTiO{sub 3} crystals

Energy Technology Data Exchange (ETDEWEB)

Stashans, Arvids [Laboratorio de Fisica, Escuela de Electronica y Telecomunicaciones, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador)]. E-mail: arvids@utpl.edu.ec; Serrano, Sheyla [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador); Escuela de Ingenierias, Universidad Politecnica Salesiana, Campus Sur, Rumichaca s/n y Moran Valverde, Apartado 17-12-536, Quito (Ecuador); Medina, Paul [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador)

2006-05-31

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO{sub 3} crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results.

Density functional theory investigation of oxygen interaction with boron-doped graphite

Energy Technology Data Exchange (ETDEWEB)

Liu, Juan; Wang, Chen [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Liang, Tongxiang, E-mail: txliang@tsinghua.edu.cn [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Lai, Wensheng [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing, 100084 (China)

2016-12-30

Highlights: • Density-functional approach is applied to study the interaction of oxygen with boron-doped graphite. • Adsorption and diffusion of oxygen atoms on boron doped graphite surfaces are studied. • Recombination of oxygen is investigated by ER and LH mechanisms. • Low boron concentration facilitates O{sub 2} formation while high boron loading inhibits the recombination. • The presence of B−B bonds due to boron accumulation makes it impossible for oxygen recombination. - Abstract: Boron inserted as impurity by substitution of carbon atoms in graphite is known to change (improve or deteriorate) oxidation resistance of nuclear graphite, but the reason for both catalytic and inhibiting oxidation is still uncertain. As a first step, this work is more specially devoted to the adsorption and diffusion of oxygen atoms on the surface and related to the problem of oxygen retention on the pure and boron-containing graphite surfaces. Adsorption energies and energy barriers associated to the diffusion for molecular oxygen recombination are calculated in the density functional theory framework. The existence of boron modifies the electronic structure of the surface, which results in an increase of the adsorption energy for O. However, low boron loading makes it easier for the recombination into molecular oxygen. For high boron concentration, it induces a better O retention capability in graphite because the presence of B-B bonds decreases recombination of the adsorbed oxygen atoms. A possible explanation for both catalytic and inhibiting effects of boron in graphite is proposed.

Determination of chemical oxygen demand (COD) using an alternative wet chemical method free of mercury and dichromate.

Science.gov (United States)

Kolb, Marit; Bahadir, Müfit; Teichgräber, Burkhard

2017-10-01

Worldwide, the standard methods for the determination of the important wastewater parameter chemical oxygen demand (COD) are still based on the use of the hazardous chemicals, mercury sulfate and chromium(VI). However, due to their properties they are meanwhile classified as "priority pollutants" and shall be phased out or banned in the frame of REACH (current European Chemical Law: Registration, Evaluation, Authorization and restriction of Chemicals) by the European Union. Hence, a new wet-chemical method free of mercury and chromium(VI) was developed. Manganese(III) was used as oxidant and silver nitrate for the removal of chloride ions. The quantification was performed by back titration of manganese(III) with iron(II) as done in the standard method. In order to minimize losses of organic substances during the precipitation of silver chloride, suspended and colloid organic matter had to be separated by precipitation of aluminum hydroxide in a first step. In these cases, two fractions, one of the suspended and colloid matters and a second of the dissolved organic substances, are prepared and oxidized separately. The method was tested with potassium hydrogen phthalate (KHP) as conventional COD reference substance and different types of wastewater samples. The oxidation of KHP was reproducible in a COD range of 20-500 mg/L with a mean recovery rate of 88.7% in comparison to the standard COD method (DIN 38409-41). Also in presence of 1000 mg/L chloride a recovery rate of 84.1% was reached. For a series of industrial and municipal wastewater samples a high correlation (R 2  = 0.9935) to the standard method with a mean recovery rate of 78.1% (±5.2%) was determined. Even though the results of the new method are not 100% of the standard method, its high correlation to the standard method and reproducibility offers an environmentally benign alternative method with no need to purchase new laboratory equipment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of lithium diffused radiation resistant solar cells, part 2

Science.gov (United States)

Payne, P. R.; Somberg, H.

1971-01-01

The work performed to investigate the effect of various process parameters on the performance of lithium doped P/N solar cells is described. Effort was concentrated in four main areas: (1) the starting material, (2) the boron diffusion, (3) the lithium diffusion, and (4) the contact system. Investigation of starting material primarily involved comparison of crucible grown silicon (high oxygen content) and Lopex silicon (low oxygen content). In addition, the effect of varying growing parameters of crucible grown silicon on lithium cell output was also examined. The objective of the boron diffusion studies was to obtain a diffusion process which produced high efficiency cells with minimal silicon stressing and could be scaled up to process 100 or more cells per diffusion. Contact studies included investigating sintering of the TiAg contacts and evaluation of the contact integrity.

Significance of the molecular diffusion for chemical and isotopic separation during the formation and degradation of natural gas reservoirs

International Nuclear Information System (INIS)

Hermichen, W.D.; Schuetze, H.

1987-01-01

Investigations at natural gas fields as well as modelling experiments have pointed out that changes of the chemical and isotopic composition occur in the course of migration, accumulation and dispersion of natural gas. Dissolution and sorption processes as well as in particular the diffusion process are considered to be the elementary separation processes. The influences on dissolved and freely flowing gases and on stationary gas accumulation are described by differential equations. The simulation of the following phenomena is shown: (1) immigration of gas into the pore space which is hydrodynamically passive, (2) diffusive migration of gas into the environment of the accumulation, and (3) diffusive 'decompression' into the roof and the floor of a gas bed and a gas containing subsoil water stratum, respectively. (author)

Will open ocean oxygen stress intensify under climate change?

Science.gov (United States)

Gnanadesikan, A.; Dunne, J. P.; John, J.

2011-07-01

Global warming is expected to reduce oxygen solubility and vertical exchange in the ocean, changes which would be expected to result in an increase in the volume of hypoxic waters. A simulation made with a full earth system model with dynamical atmosphere, ocean, sea ice and biogeochemical cycling shows that this holds true if the condition for hypoxia is set relatively high. However, the volume of the most hypoxic waters does not increase under global warming, as these waters actually become more oxygenated. We show that the rise in oxygen is associated with a drop in ventilation time. A term-by-term analysis within the least oxygenated waters shows an increased supply of oxygen due to lateral diffusion. compensating an increase in remineralization within these highly hypoxic waters. This lateral diffusive flux is the result of an increase of ventilation along the Chilean coast, as a drying of the region under global warming opens up a region of wintertime convection in our model.

Assessment of the oxygen consumption in the backfill. Geochemical modelling in a saturated backfill

International Nuclear Information System (INIS)

Grandia, Fidel; Domenech, Cristina; Arcos, David; Duro, Lara

2006-11-01

The consumption of oxygen in the deep disposal is a major concern due to the ability of this element to corrode the canisters where high level nuclear wastes (HLNW) are disposed. The anoxic conditions initially present in a deep geologic environment are disturbed by the excavation of the repository facilities. After sealing the deposition holes and tunnels using clay-based materials, oxygen remains dissolved in porewater or as a gas phase in the unsaturated pores. The main mechanisms of oxygen depletion that can be considered in the backfill materials are: (1) diffusion into the surrounding rock and (2) kinetic reactions with accessory minerals and organic matter existing in the backfill. In this report, a set of numerical simulations are carried out in one and two dimensions in order to test the effect on the oxygen concentration in the pore water of all these mechanisms. The backfill considered is a 0/70 mixture of MX-80 bentonite and crushed material from the excavation itself. In addition to organic matter, the solid phases with reducing capacity in the backfill are Fe(II)-bearing minerals: pyrite (FeS 2 ) and siderite (FeCO) (as accessory minerals in the bentonite) and Fe-biotite (from the crushed granite). In the simulations, other chemical processes like cation exchange and surface complexation onto clay surfaces, and thermodynamic equilibrium with calcite, gypsum and quartz are considered. Initial composition of porewater is obtained by equilibrating the Forsmark groundwater with the backfill material. The 1D simulation consists of a number of cells with no reactive minerals or organic matter representing granite. The central cell, however, contains oxygen and reactive minerals resembling a backfill. Oxygen is allowed to move only by diffusion. The 2D model simulates the interaction with a backfill of a granitic groundwater flowing through a fracture. Like in the 1D model, the backfill contains oxygen and reactive solids. The results are very similar in

Assessment of the oxygen consumption in the backfill. Geochemical modelling in a saturated backfill

Energy Technology Data Exchange (ETDEWEB)

Grandia, Fidel; Domenech, Cristina; Arcos, David; Duro, Lara [Enviros Spain S.L., Barcelona (Spain)

2006-11-15

The consumption of oxygen in the deep disposal is a major concern due to the ability of this element to corrode the canisters where high level nuclear wastes (HLNW) are disposed. The anoxic conditions initially present in a deep geologic environment are disturbed by the excavation of the repository facilities. After sealing the deposition holes and tunnels using clay-based materials, oxygen remains dissolved in porewater or as a gas phase in the unsaturated pores. The main mechanisms of oxygen depletion that can be considered in the backfill materials are: (1) diffusion into the surrounding rock and (2) kinetic reactions with accessory minerals and organic matter existing in the backfill. In this report, a set of numerical simulations are carried out in one and two dimensions in order to test the effect on the oxygen concentration in the pore water of all these mechanisms. The backfill considered is a 0/70 mixture of MX-80 bentonite and crushed material from the excavation itself. In addition to organic matter, the solid phases with reducing capacity in the backfill are Fe(II)-bearing minerals: pyrite (FeS{sub 2}) and siderite (FeCO) (as accessory minerals in the bentonite) and Fe-biotite (from the crushed granite). In the simulations, other chemical processes like cation exchange and surface complexation onto clay surfaces, and thermodynamic equilibrium with calcite, gypsum and quartz are considered. Initial composition of porewater is obtained by equilibrating the Forsmark groundwater with the backfill material. The 1D simulation consists of a number of cells with no reactive minerals or organic matter representing granite. The central cell, however, contains oxygen and reactive minerals resembling a backfill. Oxygen is allowed to move only by diffusion. The 2D model simulates the interaction with a backfill of a granitic groundwater flowing through a fracture. Like in the 1D model, the backfill contains oxygen and reactive solids. The results are very similar in

ESTIMATION OF INDUSTRIAL WASTE SAFETY BY THE “CHEMICAL OXYGEN DEMAND” INDEX

Directory of Open Access Journals (Sweden)

A. S. Kayshev

2015-01-01

Full Text Available One of the indices of industrial waste safety including distillers grains is chemical oxygen demand (COD, and its value (53591÷64184 mg O/dm3 shows that it can be considered as unsustainable waste. This high value of COD is conditioned by the absence of toxins in distillers grains, and by concentration of biologically active substances after which isolation the distillers grains index lowers by 74%. This allows considering the distillers grains as environmentally safe. The results received evidence the necessity for consideration of COD index only as an index of oxidized substances, but not the criteria of waste pollution.

Carbon diffusion in uncoated and titanium nitride coated iron substrates during microwave plasma assisted chemical vapor deposition of diamond

International Nuclear Information System (INIS)

Weiser, P.S.; Prawer, S.; Manory, R.R.; Paterson, P.J.K.; Stuart, Sue-Anne

1992-01-01

Auger Electron Spectroscopy has been employed to investigate the effectiveness of thin films of TiN as barriers to carbon diffusion during Chemical Vapor Deposition (CVD) of diamond onto Fe substrates. Auger Depth Profiling was used to monitor the C concentration in the TiN layer, through the interface and into the substrate both before and after CVD diamond deposition. The results show that a layer of TiN only 250 Angstroems thick is sufficient to inhibit soot formation on the Fe surface and C diffusion into the Fe bulk. 14 refs., 4 figs

Elastic neutron diffuse scattering in Zr(Ca, Y)O2-x

International Nuclear Information System (INIS)

Barberis, P.; Beuneu, B.; Novion, C.H. de.

1990-01-01

Elastic neutron diffuse scattering has been measured in cubic Zr(Ca, Y)O 2-x at room temperature. The very high diffuse scattering (up to 70 Laue) is explained mostly by the oxygen displacements along directions, and by Ca displacements along . The weak short-range order contribution strongly suggests that oxygen vacancies tend to place as second rather than at first neighbours of a Ca stabilizing ion

Oxygen isotope exchange in La2NiO(4±δ).

Science.gov (United States)

Ananyev, M V; Tropin, E S; Eremin, V A; Farlenkov, A S; Smirnov, A S; Kolchugin, A A; Porotnikova, N M; Khodimchuk, A V; Berenov, A V; Kurumchin, E Kh

2016-04-07

Oxygen surface exchange kinetics and diffusion have been studied by the isotope exchange method with gas phase equilibration using a static circulation experimental rig in the temperature range of 600-800 °C and oxygen pressure range of 0.13-2.5 kPa. A novel model which takes into account distributions of the dissociative adsorption and incorporation rates has been developed. The rates of the elementary stages have been calculated. The rate-determining stages for a La2NiO(4±δ) polycrystalline specimen have been discussed. The diffusion activation energies calculated using the gas phase equilibration method (1.4 eV) differ significantly from those calculated using isotope exchange depth profiling (0.5-0.8 eV), which was attributed to the influence of different oxygen diffusion pathways.

Influence of alloying on hydrogen-assisted cracking and diffusible ...

Indian Academy of Sciences (India)

M. Senthilkumar (Newgen Imaging) 1461 1996 Oct 15 13:05:22

moisture in the welding consumables which dissociate in the welding arc to form hydrogen and oxygen. The susceptibility of the weldment to HAC is assessed from the hydrogen diffused out from the weld after the welding is over. Hydrogen thus diffused out is referred to as diffusible hydrogen (HD) and is estimated from the ...

Development of a thermo-kinetic diffusion model for UO2 and (U,Pu)O2 oxide fuels using the DICTRA code

International Nuclear Information System (INIS)

Moore, Emily Elaine

2013-01-01

model describing the thermodynamic and kinetic properties of (U,Pu)O 2±x is currently not in existence. The aim of this work is to construct a diffusion model with DICTRA, which considers the mobility of the oxide components across non-stoichiometric ranges described by experimentally and theoretically available data. The coupling of a purely thermodynamic description provided by Gibbs energies, to the mobility model developed here presents a complete basis for describing atomic transport. A vacancy and interstitial model of diffusion is applied to the U-O and Pu-O systems as a function of their defect structure derived from CALPHAD-type thermodynamic descriptions. Self-diffusion coefficients are assessed and compared to available data. A good agreement between our calculated values for self and chemical diffusion coefficients and literature data is achieved for the binary systems. The chemical diffusion coefficients in the (U,Pu)O 2±x are extrapolated using the binary databases and are on the same order of magnitude as literature data. We evaluate defect migration energies of oxygen as a function of stoichiometric deviation. The diffusion coefficients of the stoichiometric oxides provide information containing the activation energy for diffusion as well as Frenkel pair-formation, for which our extracted values are in good agreement with available literature data. Further validation of the model includes simulations of chemical gradients imposed either at the surface to simulate reduction kinetics (UO 2+x ) or by introducing a diffusion couple (MOX) where oxygen diffusion profiles are measured as a function of distance. Both examples are in agreement with the experimental data after which the simulation conditions were reproduced. (author) [fr

Combined diffusion-weighted, blood oxygen level-dependent, and dynamic contrast-enhanced MRI for characterization and differentiation of renal cell carcinoma.

Science.gov (United States)

Notohamiprodjo, Mike; Staehler, Michael; Steiner, Nicole; Schwab, Felix; Sourbron, Steven P; Michaely, Henrik J; Helck, Andreas D; Reiser, Maximilian F; Nikolaou, Konstantin

2013-06-01

To investigate a multiparametric magnetic resonance imaging (MRI) approach comprising diffusion-weighted imaging (DWI), blood oxygen-dependent (BOLD), and dynamic contrast-enhanced (DCE) MRI for characterization and differentiation of primary renal cell carcinoma (RCC). Fourteen patients with clear-cell carcinoma and four patients with papillary RCC were examined with DWI, BOLD MRI, and DCE MRI at 1.5T. The apparent diffusion coefficient (ADC) was calculated with a monoexponential decay. The spin-dephasing rate R2* was derived from parametric R2* maps. DCE-MRI was analyzed using a two-compartment exchange model allowing separation of perfusion (plasma flow [FP] and plasma volume [VP]), permeability (permeability surface area product [PS]), and extravascular extracellular volume (VE). Statistical analysis was performed with Wilcoxon signed-rank test, Pearson's correlation coefficient, and receiver operating characteristic curve analysis. Clear-cell RCC showed higher ADC and lower R2* compared to papillary subtypes, but differences were not significant. FP of clear-cell subtypes was significantly higher than in papillary RCC. Perfusion parameters showed moderate but significant inverse correlation with R2*. VE showed moderate inverse correlation with ADC. Fp and Vp showed best sensitivity for histological differentiation. Multiparametric MRI comprising DWI, BOLD, and DCE MRI is feasible for assessment of primary RCC. BOLD moderately correlates to DCE MRI-derived perfusion. ADC shows moderate correlation to the extracellular volume, but does not correlate to tumor oxygenation or perfusion. In this preliminary study DCE-MRI appeared superior to BOLD and DWI for histological differentiation. Copyright © 2013 AUR. Published by Elsevier Inc. All rights reserved.

Chemically-induced liquid film migration with low lattice diffusivity relative to the migration rate in Mo-Ni-(W)

International Nuclear Information System (INIS)

Lee, K.R.

1992-01-01

This paper reports that when a 90Mo-10Ni alloy (by wt) liquid phase sintered at 1400 degrees C is heat-treated at 1400 degrees C after replacing the matrix with a melt of 44Ni-34Mo-22W (by wt), the liquid films between the grains migrate, leaving behind an Mo alloy enriched with W. The ratio of the lattice diffusivity of W in Mo, D, to the initial migration velocity, v. (D/v) is estimated to be between 0.03 and 0.18 angstrom. Hence it appears that there is no lattice diffusion of W ahead of the migrating liquid film, and is such a case the driving force has been suggested to be the chemical free energy. But the observed v is approximately same as that to be expected if the driving force is assumed to be diffusional coherency strain energy. Likewise, a previous study of den Broeder and Nakahara shows that the rate of chemically-induced grain boundary migration in Cu-Ni shows a smooth variation with temperature as D/v decreases from values much larger than the interatomic spacing to values much smaller with decreasing temperature. The coherency strain energy thus appears to be a general driving force for the migration even when the apparent diffusion length indicated by D/v is smaller than the interatomic spacing

A mechanistic model for long-term nuclear waste glass dissolution integrating chemical affinity and interfacial diffusion barrier

Energy Technology Data Exchange (ETDEWEB)

Ma, Teqi [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China); Mechanics and Physics of Solids Research Group, Modelling and Simulation Centre, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Jivkov, Andrey P., E-mail: andrey.jivkov@manchester.ac.uk [Mechanics and Physics of Solids Research Group, Modelling and Simulation Centre, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Li, Weiping; Liang, Wei; Wang, Yu; Xu, Hui [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China); Han, Xiaoyuan, E-mail: xyhan_nint@sina.cn [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China)

2017-04-01

Understanding the alteration of nuclear waste glass in geological repository conditions is critical element of the analysis of repository retention function. Experimental observations of glass alterations provide a general agreement on the following regimes: inter-diffusion, hydrolysis process, rate drop, residual rate and, under very particular conditions, resumption of alteration. Of these, the mechanisms controlling the rate drop and the residual rate remain a subject of dispute. This paper offers a critical review of the two most competitive models related to these regimes: affinity–limited dissolution and diffusion barrier. The limitations of these models are highlighted by comparison of their predictions with available experimental evidence. Based on the comprehensive discussion of the existing models, a new mechanistic model is proposed as a combination of the chemical affinity and diffusion barrier concepts. It is demonstrated how the model can explain experimental phenomena and data, for which the existing models are shown to be not fully adequate.

Chemical identities of radioiodine released from U3O8 in oxygen and inert gas atmospheres

International Nuclear Information System (INIS)

Tachikawa, E.; Nakashima, M.

1977-01-01

Irradiated U 3 O 8 was heated from room temperature to 1100 0 C in a temperature-programmed oven (5 0 C/min) in a flow of carrier gas. The iodine released to an inert gas was deposited in the temperature range from 200 to 300 0 C with a peak at 250 0 C (speciesA). This species is neither in a form combined with other fission products nor in elemental form. It is possibly a chemical combination with uranium. It reacts with oxygen, yielding species B characterized by its deposition at a temperature close to room temperature. The activation energy of this oxidation reaction was determined to be 6.0 +-0.5 Kcal/mol. Comparing the deposition-profile with those obtained with carrier-free I 2 and HI indicated that species B was I 2 . As for the formation of organic iodides accompanying the release in an inert gas, it was concluded that these were produced in radical reactions. Thus, in a presence of oxygen, organic iodides were formed in competition with the reactions of organic radicals with oxygen. (author)

The structural evolution and diffusion during the chemical transformation from cobalt to cobalt phosphide nanoparticles

KAUST Repository

Ha, Don-Hyung

2011-01-01

We report the structural evolution and the diffusion processes which occur during the phase transformation of nanoparticles (NPs), ε-Co to Co 2P to CoP, from a reaction with tri-n-octylphosphine (TOP). Extended X-ray absorption fine structure (EXAFS) investigations were used to elucidate the changes in the local structure of cobalt atoms which occur as the chemical transformation progresses. The lack of long-range order, spread in interatomic distances, and overall increase in mean-square disorder compared with bulk structure reveal the decrease in the NP\\'s structural order compared with bulk structure, which contributes to their deviation from bulk-like behavior. Results from EXAFS show both the Co2P and CoP phases contain excess Co. Results from EXAFS, transmission electron microscopy, X-ray diffraction, and density functional theory calculations reveal that the inward diffusion of phosphorus is more favorable at the beginning of the transformation from ε-Co to Co2P by forming an amorphous Co-P shell, while retaining a crystalline cobalt core. When the major phase of the sample turns to Co 2P, the diffusion processes reverse and cobalt atom out-diffusion is favored, leaving a hollow void, characteristic of the nanoscale Kirkendall effect. For the transformation from Co2P to CoP theory predicts an outward diffusion of cobalt while the anion lattice remains intact. In real samples, however, the Co-rich nanoparticles continue Kirkendall hollowing. Knowledge about the transformation method and structural properties provides a means to tailor the synthesis and composition of the NPs to facilitate their use in applications. © 2011 The Royal Society of Chemistry.

Convergence to equilibrium of renormalised solutions to nonlinear chemical reaction–diffusion systems

Science.gov (United States)

Fellner, Klemens; Tang, Bao Quoc

2018-06-01

The convergence to equilibrium for renormalised solutions to nonlinear reaction-diffusion systems is studied. The considered reaction-diffusion systems arise from chemical reaction networks with mass action kinetics and satisfy the complex balanced condition. By applying the so-called entropy method, we show that if the system does not have boundary equilibria, i.e. equilibrium states lying on the boundary of R_+^N, then any renormalised solution converges exponentially to the complex balanced equilibrium with a rate, which can be computed explicitly up to a finite-dimensional inequality. This inequality is proven via a contradiction argument and thus not explicitly. An explicit method of proof, however, is provided for a specific application modelling a reversible enzyme reaction by exploiting the specific structure of the conservation laws. Our approach is also useful to study the trend to equilibrium for systems possessing boundary equilibria. More precisely, to show the convergence to equilibrium for systems with boundary equilibria, we establish a sufficient condition in terms of a modified finite-dimensional inequality along trajectories of the system. By assuming this condition, which roughly means that the system produces too much entropy to stay close to a boundary equilibrium for infinite time, the entropy method shows exponential convergence to equilibrium for renormalised solutions to complex balanced systems with boundary equilibria.

Enhanced oxygen diffusion in low barium-containing La0.2175Pr0.2175Ba0.145Sr0.4Fe0.8Co0.2O3−δ intermediate temperature solid oxide fuel cell cathodes

KAUST Repository

Vert, Vicente B.; Serra, José M.; Kilner, John A.; Burriel, Mó nica

2012-01-01

Isotopic tracer diffusion studies have been performed on the perovskite composition La 0.2175Pr 0.2175Ba 0.145Sr 0.4Fe 0.8Co 0.2O 3-δ to obtain the diffusion and surface exchange coefficients for oxygen. This material has been identified as a highly

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

Science.gov (United States)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

Oxygen ordering and superconductivity in the high Tc superconductor YBa2Cu3O6+x

International Nuclear Information System (INIS)

Friis Poulsen, H.

1991-12-01

This report contains the result of an experimental and theoretical investigation of the oxygen ordering process in the High T c superconductor Y Ba 2 Cu 3 O 6+x . Neutron scattering is used in connection with in situ monitoring of the oxygen in-diffusion in a gas-volumetric equipment. Information on the variations of the structural phases, the twin domain sizes, the elastic forces, the chemical potential og oxygen as well as diffusion are provided. Using Monte Carlo simulations we find that a simple two-dimentional lattice gas model of the oxygen ordering process, the ASYNNNI model, gives an excellent description of the vast majority of these data. A systematic study of the relationship between the static and dynamic variations of the superconducting transition temperature, T c , and the corresponding variations of the low temperature oxygen ordering process is performed. Statistics from Monte Carlo simulations based on the ASYNNNI model are combined with experimental data from the literature. The combined static and dynamic analysis makes it evident that within a charge transfer model, a linear T c versus charge transfer relationship can only be rationalized if the description is based on extended coherent ordered domains and if the dynamic co-existence between the Ortho-I and the Ortho-II type of domains inherent to the ASYNNNI model is taken into account. A minimal model is proposed, where the total charge transfer is found as a weighted sum over the areas of the Ortho-I and the Ortho-II domains, and the minimal size of the two types of domains are given by a doubling og their unit cells in both directions. (au) 5 tabs., 35 ills., 108 refs

Surface exchange kinetics and chemical diffusivities of BaZr{sub 0.2}Ce{sub 0.65}Y{sub 0.15}O{sub 3−δ} by electrical conductivity relaxation

Energy Technology Data Exchange (ETDEWEB)

Lim, Dae-Kwang; Jeon, Sang-Yun; Singh, Bhupendra [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of); Park, Jun-Young [Department of Advanced Materials Engineering, Sejong University, Seoul 143-747 (Korea, Republic of); Song, Sun-Ju, E-mail: song@chonnam.ac.kr [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of)

2014-10-15

Highlights: • Electrical conductivity relaxation in BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} was monitored. • Monotonic relaxation behavior was observed during oxidation/reduction. • Nonmonotonic twofold relaxation behavior was observed during hydration/dehydration. • Surface exchange coefficients and diffusivities of O and H were calculated. - Abstract: Perovskite-type oxide BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} (BCZY2015) was synthesized by a solid state reaction method. BCZY2015 samples were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The time dependent variation in electrical conductivity of BCZY2015 was monitored during the oxidation/reduction in oxygen partial pressure (pO{sub 2}) range of −2.28 ⩽ log (pO{sub 2}/atm) ⩽ −0.68 at a fixed water vapor pressure (pH{sub 2}O), and during the hydration/dehydration in −3.15 ⩽ log (pH{sub 2}O/atm) ⩽ −2.35 range in air. The electrical conductivity showed a monotonic relaxation behavior by the ambipolar diffusion of V{sub o}{sup ··} and OH{sub o}{sup ·} during the oxidation/reduction and the relaxation process was governed by the diffusivity of oxygen (D-tilde{sub vO}). On the other hand, during the hydration/dehydration process, a non-monotonic twofold relaxation behavior was observed due to the decoupled diffusion of H and O components with the mediation of holes, and the conductivity relaxation process was governed by the diffusivities of both H (D-tilde{sub iH}) and O (D-tlde{sub vH}). The values of surface exchange coefficients and diffusivities of oxygen and hydrogen were calculated from Fick’s second law by the nonlinear least squares fitting of the conductivity data, as proposed by Yoo et al. (2008)

Chemical composition and properties of spray-dried sugar beet concentrate obtained after ultrafiltration of diffusion juice

Directory of Open Access Journals (Sweden)

Regiec Piotr

2015-03-01

Full Text Available Ultrafiltration of diffusion juice is a method that can reduce environmental pollution during the production of sugar. A by-product (concentrate of ultrafiltration contains a large amount of sucrose, but due to its properties, it is difficult to manage. The aim of this study was to determine the effects of the temperature used during drying of diffusion juice concentrates on the content of certain components and characteristics of resultant preparations. Diffusion juice obtained from one of the Polish sugar plants was subjected to ultrafiltration and the obtained concentrates were dried in a spray dryer. In the dried samples, the following parameters were analyzed: dry mass, sucrose, total ash, protein, crude fiber and color. It has been declared that the degree of concentration and drying temperature influenced the chemical composition and the properties of the dehydrated diffusion juice concentrates. An increase in drying temperature was accompanied by the increased content of dry mass, protein, ash and fiber content in the preparations. The greater the degree of juice concentration, the greater was the content of dry mass, ash, and fiber. Inversely, the greater the degree of juice concentration, the lower the content of sucrose. The brightest color of the dehydrated product was observed at the drying temperature of 200°C. Spray-drying may be used for waste management after the diffusion juice membrane filtration, and the resultant preparations might be used in the production of feedstuff or food industry in general e.g. as sucrose source, in fermentation processes or in microorganisms propagation.

A CHEMICAL KINETICS NETWORK FOR LIGHTNING AND LIFE IN PLANETARY ATMOSPHERES

International Nuclear Information System (INIS)

Rimmer, P. B.; Helling, Ch

2016-01-01

There are many open questions about prebiotic chemistry in both planetary and exoplanetary environments. The increasing number of known exoplanets and other ultra-cool, substellar objects has propelled the desire to detect life and prebiotic chemistry outside the solar system. We present an ion–neutral chemical network constructed from scratch, Stand2015, that treats hydrogen, nitrogen, carbon, and oxygen chemistry accurately within a temperature range between 100 and 30,000 K. Formation pathways for glycine and other organic molecules are included. The network is complete up to H6C2N2O3. Stand2015 is successfully tested against atmospheric chemistry models for HD 209458b, Jupiter, and the present-day Earth using a simple one-dimensional photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting for CO 2 , H 2 , CO, and O 2 , but do not agree for water and atomic oxygen. We use the network to simulate an experiment where varied chemical initial conditions are irradiated by UV light. The result from our simulation is that more glycine is produced when more ammonia and methane is present. Very little glycine is produced in the absence of any molecular nitrogen and oxygen. This suggests that the production of glycine is inhibited if a gas is too strongly reducing. Possible applications and limitations of the chemical kinetics network are also discussed.

A CHEMICAL KINETICS NETWORK FOR LIGHTNING AND LIFE IN PLANETARY ATMOSPHERES

Energy Technology Data Exchange (ETDEWEB)

Rimmer, P. B.; Helling, Ch, E-mail: pr33@st-andrews.ac.uk [School of Physics and Astronomy, University of St Andrews, St Andrews, KY16 9SS (United Kingdom)

2016-05-01

There are many open questions about prebiotic chemistry in both planetary and exoplanetary environments. The increasing number of known exoplanets and other ultra-cool, substellar objects has propelled the desire to detect life and prebiotic chemistry outside the solar system. We present an ion–neutral chemical network constructed from scratch, Stand2015, that treats hydrogen, nitrogen, carbon, and oxygen chemistry accurately within a temperature range between 100 and 30,000 K. Formation pathways for glycine and other organic molecules are included. The network is complete up to H6C2N2O3. Stand2015 is successfully tested against atmospheric chemistry models for HD 209458b, Jupiter, and the present-day Earth using a simple one-dimensional photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting for CO{sub 2}, H{sub 2}, CO, and O{sub 2}, but do not agree for water and atomic oxygen. We use the network to simulate an experiment where varied chemical initial conditions are irradiated by UV light. The result from our simulation is that more glycine is produced when more ammonia and methane is present. Very little glycine is produced in the absence of any molecular nitrogen and oxygen. This suggests that the production of glycine is inhibited if a gas is too strongly reducing. Possible applications and limitations of the chemical kinetics network are also discussed.

Nitritation performance and biofilm development of co- and counter-diffusion biofilm reactors: Modeling and experimental comparison

DEFF Research Database (Denmark)

Wang, Rongchang; Terada, Akihiko; Lackner, Susanne

2009-01-01

A comparative study was conducted on the start-up performance and biofilm development in two different biofilm reactors with aim of obtaining partial nitritation. The reactors were both operated under oxygen limited conditions, but differed in geometry. While substrates (O-2, NH3) co......-diffused in one geometry, they counter-diffused in the other. Mathematical simulations of these two geometries were implemented in two 1-D multispecies biofilm models using the AQUASIM software. Sensitivity analysis results showed that the oxygen mass transfer coefficient (K-i) and maximum specific growth rate...... results showed that the counter-diffusion biofilms developed faster and attained a larger maximum biofilm thickness than the co-diffusion biofilms. Under oxygen limited condition (DO

Yeast alter micro-oxygenation of wine: oxygen consumption and aldehyde production.

Science.gov (United States)

Han, Guomin; Webb, Michael R; Richter, Chandra; Parsons, Jessica; Waterhouse, Andrew L

2017-08-01

Micro-oxygenation (MOx) is a common winemaking treatment used to improve red wine color development and diminish vegetal aroma, amongst other effects. It is commonly applied to wine immediately after yeast fermentation (phase 1) or later, during aging (phase 2). Although most winemakers avoid MOx during malolactic (ML) fermentation, it is often not possible to avoid because ML bacteria are often present during phase 1 MOx treatment. We investigated the effect of common yeast and bacteria on the outcome of micro-oxygenation. Compared to sterile filtered wine, Saccharomyces cerevisiae inoculation significantly increased oxygen consumption, keeping dissolved oxygen in wine below 30 µg L -1 during micro-oxygenation, whereas Oenococcus oeni inoculation was not associated with a significant impact on the concentration of dissolved oxygen. The unfiltered baseline wine also had both present, although with much higher populations of bacteria and consumed oxygen. The yeast-treated wine yielded much higher levels of acetaldehyde, rising from 4.3 to 29 mg L -1 during micro-oxygenation, whereas no significant difference was found between the bacteria-treated wine and the filtered control. The unfiltered wine exhibited rapid oxygen consumption but no additional acetaldehyde, as well as reduced pyruvate. Analysis of the acetaldehyde-glycerol acetal levels showed a good correlation with acetaldehyde concentrations. The production of acetaldehyde is a key outcome of MOx and it is dramatically increased in the presence of yeast, although it is possibly counteracted by the metabolism of O. oeni bacteria. Additional controlled experiments are necessary to clarify the interaction of yeast and bacteria during MOx treatments. Analysis of the glycerol acetals may be useful as a proxy for acetaldehyde levels. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Rapid determination of oxygen saturation and vascularity for cancer detection.

Directory of Open Access Journals (Sweden)

Fangyao Hu

Full Text Available A rapid heuristic ratiometric analysis for estimating tissue hemoglobin concentration and oxygen saturation from measured tissue diffuse reflectance spectra is presented. The analysis was validated in tissue-mimicking phantoms and applied to clinical measurements in head and neck, cervical and breast tissues. The analysis works in two steps. First, a linear equation that translates the ratio of the diffuse reflectance at 584 nm and 545 nm to estimate the tissue hemoglobin concentration using a Monte Carlo-based lookup table was developed. This equation is independent of tissue scattering and oxygen saturation. Second, the oxygen saturation was estimated using non-linear logistic equations that translate the ratio of the diffuse reflectance spectra at 539 nm to 545 nm into the tissue oxygen saturation. Correlations coefficients of 0.89 (0.86, 0.77 (0.71 and 0.69 (0.43 were obtained for the tissue hemoglobin concentration (oxygen saturation values extracted using the full spectral Monte Carlo and the ratiometric analysis, for clinical measurements in head and neck, breast and cervical tissues, respectively. The ratiometric analysis was more than 4000 times faster than the inverse Monte Carlo analysis for estimating tissue hemoglobin concentration and oxygen saturation in simulated phantom experiments. In addition, the discriminatory power of the two analyses was similar. These results show the potential of such empirical tools to rapidly estimate tissue hemoglobin in real-time spectral imaging applications.

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

Science.gov (United States)

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

Mechanism of pulse discharge production of iodine atoms from CF3I molecules for a chemical oxygen-iodine laser

International Nuclear Information System (INIS)

Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

2009-01-01

The pulsed chemical oxygen-iodine laser (COIL) development is aimed at many new applications. Pulsed electric discharge is most effective in turning COIL operation into the pulse mode by instant production of iodine atoms. A numerical model is developed for simulations of the pulsed COIL initiated by an electric discharge. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are found by solving the electron Boltzmann equation, which is re-calculated in a course of computations when plasma parameters changed. The processes accounted for in the Boltzmann equation include excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions, second-kind collisions and stepwise excitation of molecules. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. Results of numerical simulations are compared with experimental laser pulse waveforms. It is concluded that there is satisfactory agreement between theory and the experiment. The prevailing mechanism of iodine atom formation from the CF 3 I donor in a very complex kinetic system of the COIL medium under pulse discharge conditions, based on their detailed numerical modelling and by comparing these results both with experimental results of other authors and their own experiments, is established. The dominant iodine atom production mechanism for conditions under study is the electron-impact dissociation of CF 3 I molecules. It was proved that in the conditions of the experiment the secondary chemical reactions with O atoms play an insignificant role.

Screening of NiFe₂O₄ Nanoparticles as Oxygen Carrier in Chemical Looping Hydrogen Production

DEFF Research Database (Denmark)

Liu, Shuai; He, Fang; Huang, Zhen

2016-01-01

) methods were used to prepare NiFe2O4 oxygen carriers. Samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurement, as well as Barrett-Joyner-Halenda (BJH......The objective of this paper is to systematically investigate the influences of different preparation methods on the properties of NiFe2O4 nanoparticles as oxygen carrier in chemical looping hydrogen production (CLH). The solid state (SS), coprecipitation (CP), hydrothermal (HT), and sol-gel (SG...... gas (24% H2 + 24% CO + 12% CO2 + N2 balance), then reacted with steam to produce H2, and finally fully oxidized by air. The NiFe2O4 oxygen carrier prepared by the sol gel method showed the best capacity for hydrogen production and the highest recovery degree of lattice oxygen, in agreement...

Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

Science.gov (United States)

Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

2018-03-01

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Kinetic of the Oxygen Control System (OCS) for stagnant lead-bismuth systems

International Nuclear Information System (INIS)

Lefhalm, C.H.; Knebel, J.U.; Mack, K.J.

2001-09-01

Within the framework of the HGF strategy fund project 99/16 ''Thermalhydraulic and Material Specific Investigations into the Realization of an accelerator driven system (ADS) to Transmute Minor Actinides'' at the institute for nuclear and energy technology (IKET) investigations on the cooling of thermally high-loaded surfaces with liquid lead bismuth (Pb-Bi) are carried out. To operate a Pb-Bi loop safety, for example in order to cool a spallation target or a blanket of an accelerator driven system (ADS), the control of the oxygen concentration within the liquid metal is an inalienable prerequisite to prevent or minimize corrosion at the structure material. In this report the kinetic behaviour of the oxygen control system (OCS), which was developed at Forschungszentrum Karlsruhe, is examined. The OCS controls the chemical potential of oxygen in the liquid metal by regulating the oxygen content in the gas phase which flows over the free surface of the liquid metal. In this work the experimental facility KOCOS (kinetics of oxygen control system) in the karlsruhe lead laboratory (KALLA) was built. A physical diffusion model was utilised and extended to describe the exchange of oxygen between the gas and the liquid metal. The theoretical calculations are in very good agreement to the experimental findings. The OCS allows to control reversibly the oxygen concentration in the liquid metal. According to the observed kinetics of the process one can extrapolate that the control of large volumes, as they are necessary to operate an ADS demonstrator, is possible. Therefore, further experiments in liquid metal loop systems are suggested. (orig.)

Study of cation diffusion in Zn O using 65Zn as radioactive tracer

International Nuclear Information System (INIS)

Ferraz, Wilmar B.; Correa, Ricardo F.; Nogueira, Maria A.N.; Ramos, Marcelo; Sabioni, Antonio C.S.

2000-01-01

Zinc self-diffusion coefficient were measured in polycrystalline Zn O of high purity (99,999%) prepared by conventional sintering at 1393 deg C, 4 h, in oxygen atmosphere. The Zn O samples had high density (>99% of the theoretical density) and grain size of 20 μm. These samples were resintered for 72 h at 1400 deg C in order to increase the grain-size higher than 50 μ m. Samples of 15 x 15 x 2 mm 3 were polished with diamond paste, and pre-annealed under the same conditions of temperature and atmosphere of the diffusion annealing. A thin film of 65 Zn - radioactive tracer - applied to the polished surface was oxidized in oxygen atmosphere for a short time before diffusion annealing. The diffusion experiments were performed between 1002 and 1201 deg C in oxygen atmosphere. The 65 Zn diffusion profiles were measured by sectioning in conjunction with residual-activity measurements. The results of the determination of the zinc in Zn O diffusion coefficients in function of temperature are presented and a comparison of these results obtained by the two radioactive method is showed. (author)

Oxygen gradients in tissue-engineered PEGT/PBT cartilaginous constructs: Measurement and modeling

NARCIS (Netherlands)

Malda, J.; Rouwkema, Jeroen; Martens, D.E.; le Comte, EP; Kooy, F.K.; Tramper, J.; van Blitterswijk, Clemens; Riesle, J.U.

2004-01-01

The supply of oxygen within three-dimensional tissue-engineered (TE) cartilage polymer constructs is mainly by diffusion. Oxygen consumption by cells results in gradients in the oxygen concentration. The aims of this study were, firstly, to identify the gradients within TE cartilage polymer

Oxygen gradients in tissue-engineered PEGT/PBT cartilaginous constructs: measurement and modeling

NARCIS (Netherlands)

Malda, J.; Rouwkema, J.; Martens, D.E.; Paul le Comte, E.; Kooy, F.K.; Tramper, J.; Blitterswijk, van C.A.; Riesle, J.

2004-01-01

The supply of oxygen within three-dimensional tissue-engineered (TE) cartilage polymer constructs is mainly by diffusion. Oxygen consumption by cells results in gradients in the oxygen concentration. The aims of this study were, firstly, to identify the gradients within TE: cartilage polymer

Oxygen as a product of water radiolysis in high-LET tracks. II. Radiobiological implications

International Nuclear Information System (INIS)

Baverstock, K.F.; Burns, W.G.

1981-01-01

Consideration is given to the possibility that molecular oxygen generated in the tracks of energetic heavy ions is responsible for the reduction in oxygen enhancement ratio (OER) with increasing linear energy transfer (LET) observed for the loss of reproductive capacity caused by radiation in many cellular organisms. Yields of oxygen relationship of OER to LET for two organisms, Chlamydomonas reinhardii and Shigella flexneri, using a simple diffusion kinetic model for radiobiological action which takes account of the diffusion of oxygen after its formation. The results of these calculations show that the model accounts well for the shape of the OER vs. LET relationship

A DLTS study of the evolution of oxygen precipitates in Si at high temperature and high pressure

International Nuclear Information System (INIS)

Antonova, I.V.; Popov, V.P.; Fedina, L.I.; Shaimeev, S.S.; Misiuk, A.

1996-01-01

The effect of high hydrostatic pressure on the dissolution of oxygen precipitates introduced beforehand into Si at temperatures of 920-1000 K (over period of 96 h) is investigated by the DLTS method. A measurement procedure, based on the formation of electrically active complexes (interstitial oxygen atom-vacancy) during electron irradiation of the samples, is proposed. It is shown that the precipitates do not decompose when point defects are introduced at room temperature. As the treatment temperature increases (to 1220-1650 K), for the same values of the hydrostatic pressure (up to 1.3 GPa) the intensity of the decomposition of oxygen precipitates increases and at 1650 K they are completely dissolved. Study of the decomposition kinetics showed that hydrostatic pressure raises the limit of solubility of the oxygen atoms Oi and slows down their diffusion. It is determined that the diffusion activation energy Ea, just as the preexponential factor D0, in the expression for the diffusion decrease with increasing hydrostatic pressure, resulting in a lower diffusion. Possible mechanisms for the effect of hydrostatic pressure on oxygen diffusion near a precipitate are discussed

Oxygen penetration around burrows and roots in aquatic sediments

DEFF Research Database (Denmark)

Meysman, Filip J.R.; Galaktionov, O.S.; Glud, Ronnie N.

2010-01-01

Diffusion is the dominant physical mechanism for the transfer of oxygen into fine-grained aquatic sediments. This diffusive uptake occurs at the sediment-water interface, but also at internal interfaces, such as along ventilated burrows or O2 releasing plant roots. Here, we present a systematic...

Engineering Mixed Ionic Electronic Conduction in La 0.8 Sr 0.2 MnO 3+ δ Nanostructures through Fast Grain Boundary Oxygen Diffusivity

KAUST Repository

Saranya, Aruppukottai M.

2015-04-09

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Nanoionics has become an increasingly promising field for the future development of advanced energy conversion and storage devices, such as batteries, fuel cells, and supercapacitors. Particularly, nanostructured materials offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. However, the enhancement of the mass transport properties at the nanoscale has often been found to be difficult to implement in nanostructures. Here, an artificial mixed ionic electronic conducting oxide is fabricated by grain boundary (GB) engineering thin films of La0.8Sr0.2MnO3+δ. This electronic conductor is converted into a good mixed ionic electronic conductor by synthesizing a nanostructure with high density of vertically aligned GBs with high concentration of strain-induced defects. Since this type of GBs present a remarkable enhancement of their oxide-ion mass transport properties (of up to six orders of magnitude at 773 K), it is possible to tailor the electrical nature of the whole material by nanoengineering, especially at low temperatures. The presented results lead to fundamental insights into oxygen diffusion along GBs and to the application of these engineered nanomaterials in new advanced solid state ionics devices such are micro-solid oxide fuel cells or resistive switching memories. An electronic conductor such as La0.8Sr0.2MnO3+δ is converted into a good mixed ionic electronic conductor by synthesizing a nanostructure with excellent electronic and oxygen mass transport properties. Oxygen diffusion highways are created by promoting a high concentration of strain-induced defects in the grain boundary region. This novel strategy opens the way for synthesizing new families of artificial mixed ionic-electronic conductors by design.

Diffusion of neon in white dwarf stars.

Science.gov (United States)

Hughto, J; Schneider, A S; Horowitz, C J; Berry, D K

2010-12-01

Sedimentation of the neutron rich isotope 22Ne may be an important source of gravitational energy during the cooling of white dwarf stars. This depends on the diffusion constant for 22Ne in strongly coupled plasma mixtures. We calculate self-diffusion constants D(i) from molecular dynamics simulations of carbon, oxygen, and neon mixtures. We find that D(i) in a mixture does not differ greatly from earlier one component plasma results. For strong coupling (coulomb parameter Γ> few), D(i) has a modest dependence on the charge Z(i) of the ion species, D(i)∝Z(i)(-2/3). However, D(i) depends more strongly on Z(i) for weak coupling (smaller Γ). We conclude that the self-diffusion constant D(Ne) for 22Ne in carbon, oxygen, and neon plasma mixtures is accurately known so that uncertainties in D(Ne) should be unimportant for simulations of white dwarf cooling.

Chemical reduction of refractory oxides by atomic hydrogen

International Nuclear Information System (INIS)

Dooley, D.; Balooch, M.; Olander, D.R.

1978-11-01

The chemical reduction of UO 2 and Al 2 O 3 by atomic hydrogen was studied. Results of the UO 2 /H investigation indicates that reduction of UO 2 by atomic hydrogen proceeds by the production of water vapor and hypostoichiometric urania. Water vapor and aluminum metal are formed in the Al 2 O 3 /H system. The relative ease which UO 2 is reduced by atomic hydrogen compared with Al 2 O 3 is due to two factors. The first is related to the thermochemistry of the reactions. The second factor which favors efficient reduction of UO 2 but not of Al 2 O 3 is the oxygen diffusivity

Diffuse plasma treatment of polyamide 66 fabric in atmospheric pressure air

International Nuclear Information System (INIS)

Li, Lee; Peng, Ming-yang; Teng, Yun; Gao, Guozhen

2016-01-01

Graphical abstract: - Highlights: • A cylindrical-electrode nanosecond-pulse diffuse-discharge reactor is presented. • Large-scale non-thermal plasmas were generated steadily in atmospheric air. • Treated PA66 fabric is etched with oxygen-containing group increases. • The hydrophily of treated PA66 fabric improves effectively. • Extending the treatment time is a method to reduce the treatment frequency. - Abstract: The polyamide 66 (PA66) fabrics are hard to be colored or glued in industrial production due to the poor hydrophily. Diffuse plasma is a kind of non-thermal plasma generated at atmospheric pressure in air. This paper proposes that large-scale diffuse plasma generated between wire electrodes can be employed for improving the hydrophily of PA66 fabrics. A repetitive nanosecond-pulse diffuse-discharge reactor using a cylindrical wire electrode configuration is presented, which can generate large-scale non-thermal plasmas steadily at atmospheric pressure without any barrier dielectric. Then the reactor is used to treat PA66 fabrics in different discharge conditions. The hydrophilicity property of modified PA66 is measured by wicking test method. The modified PA66 is also analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) to prove the surface changes in physical microstructure and chemical functional groups, respectively. What's more, the effects of treatment time and treatment frequency on surface modification are investigated and discussed.

Atomic oxygen-MoS sub 2 chemical interactions

Energy Technology Data Exchange (ETDEWEB)

Cross, J.B.; Martin, J.A. (Los Alamos National Lab., NM (USA)); Pope, L.E. (Sandia National Labs., Albuquerque, NM (USA)); Koontz, S.L. (National Aeronautics and Space Administration, Johnson Space Center, Houston, TX (USA))

1990-10-01

The present study shows that an O-atom translation energy of 1.5 eV, SO{sub 2} is generated and outgases from an anhydrous MoS{sub 2} surface with an initial reactivity nearly 50% that of kapton. The reaction of atomic oxygen with MoS{sub 2} has little or no translational energy barrier, i.e. thermally generated atomic oxygen reacts as readily as that having 1.5 eV of translational energy. For MoS{sub 2} films sputter-deposited at 50-70deg C, friction measurements showed a high initial friction coefficient (up to 0.25) for MoS{sub 2} surfaces exposed to atomic oxygen, which dropped to the normal low values after several cycles of operation in air and ultrahigh vacuum. For MoS{sub 2} films deposited at 200deg C, the friction coefficient was not affected by the O-atom exposure. (orig.).

Effect of different chemical modification of carbon nanotubes for the oxygen reduction reaction in alkaline media

International Nuclear Information System (INIS)

Dumitru, Anca; Mamlouk, M.; Scott, K.

2014-01-01

The electrochemical reduction of oxygen on chemically modified multi-walled carbon nanotubes (CNTs) electrodes in 1 M KOH solution has been studied using the rotating ring disc electrode (RDE). The surface modification of CNTs has been estimated by XPS and Raman spectroscopy. The effect of different oxygen functionalities on the surface of carbon nanotube for the oxygen reduction reaction (ORR) is considered in terms of the number of electrons (n) involved. Electrochemical studies indicate that in the case of the modification of CNTs with citric acid and diazonium salts the n values were close to two in the measured potential range, and the electrochemical reduction is limited to the production of peroxide as the final product. In the case of the modification of carbon nanotubes with peroxymonosulphuric acid, in the measured potential range, the n value is close to 4 indicating the four-electron pathway for the ORR. By correlating ORR measurements with the XPS analysis, we propose that the increase in electrocatalytic activity towards the ORR, for CNT can be attributed to the increase in C-O groups on the surface of CNTs after modification with peroxymonosulphuric acid