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Sample records for b4c oxidation modelling

  1. Heat release from B4C oxidation in steam and air

    International Nuclear Information System (INIS)

    Belovsky, L.

    1996-01-01

    BWR and some PWR cores contain boron carbide (B 4 C) as neutron absorber. During a severe accident, the B 4 C can potentially react with steam under release of heat and hydrogen. Although models for B 4 C oxidation already exist in MELCOR and SCDAP/RELAP5, a development of a new model for another computer code seems to be difficult due to a missing comprehensive description of the current modelling methodology and scarce experimental data. The aim of this paper is to highlight the key points of the B 4 C oxidation using the existing available experimental data and to perform a simple heat balance analysis of the B 4 C/steam and B 4 C/air chemical reactions. The analysis of literature data shows that the B 4 C oxidation phenomenon is qualitatively well described below 1000 deg. C. However, no reliable data exist for the reaction kinetics especially above this temperature. It was found that the experimental results strongly depend on the experimental arrangement. The reaction heats, calculated in this study, indicate that the B 4 C oxidation is an exothermic reaction, releasing more heat in air than in steam. The formation of boric acids from the boron oxide increases the heat release from B 4 C by ∼ 10%, in the worst case. Although the total heat, released in a PWR core from the B 4 C oxidation, is probably much smaller than the heat released from the Zr/steam reaction, it is not excluded that the B 4 C oxidation can locally contribute to the damage of the control elements due to local overheating. Modelling of these phenomena is, however, very difficult due to the complex geometry of the liquefied control elements and due to absence of suitable data on the reaction kinetics. (author). 25 refs, 2 figs, 3 tabs

  2. Progress on B4C control rod modeling in RELAP/SCDAPSIM with application to quench and Phebus

    International Nuclear Information System (INIS)

    Kawahara, Keisuke; Hohorst, Judith K.; Allison, Chris M.

    2014-01-01

    The RELAP/SCDAPSIM code is designed to predict the behavior of reactor systems during normal and accident conditions. RELAP/SCDAPSIM/MOD3.5 is an experimental version of the code with the most advanced fuel and severe accident behavior models and correlations. It includes modeling improvements that were specifically added to support (a) the ongoing experimental severe accident programs in Europe and Japan and (b) the analysis and assessment activities related to the accident at the Fukushima Daiichi NPS. One of the improved models describes the behavior of cylindrical B 4 C control rods used in selected PWR designs and in integral experiments used to assess the heating and melting of PWR, BWR, and VVER assemblies. It replaces an older model that was originally developed by the US Nuclear Regulatory Commission in the mid- 1980's. It includes a combination of new and improved models and correlations to more accurately describe (a) eutectic reactions between Zircaloy, B 4 C, and stainless steel, (b) oxidation for B 4 C, Zircaloy, and stainless steel, and (c) the effects of the gap between the Zircaloy guide tube and the stainless steel sheath surrounding B 4 C pellets used in many control rod designs. This paper will discuss the development of the new model and validation of the model using the PHEBUS B 4 C test, FPT-3, and the KIT quench experiments with a central B 4 C control rod. (authors)

  3. Modeling of wear behavior of Al/B_4C composites produced by powder metallurgy

    International Nuclear Information System (INIS)

    Sahin, Ismail; Bektas, Asli; Guel, Ferhat; Cinci, Hanifi

    2017-01-01

    Wear characteristics of composites, Al matrix reinforced with B_4C particles percentages of 5, 10,15 and 20 produced by the powder metallurgy method were studied in this study. For this purpose, a mixture of Al and B_4C powders were pressed under 650 MPa pressure and then sintered at 635 C. The analysis of hardness, density and microstructure was performed. The produced samples were worn using a pin-on-disk abrasion device under 10, 20 and 30 N load through 500, 800 and 1200 mesh SiC abrasive papers. The obtained wear values were implemented in an artificial neural network (ANN) model having three inputs and one output using feed forward backpropagation Levenberg-Marquardt algorithm. Thus, the optimum wear conditions and hardness values were determined.

  4. Modelling of the interactions between B4C and stainless steel at high temperatures

    International Nuclear Information System (INIS)

    Veshchunov, M.S.

    1995-01-01

    Results of detailed chemical-analytical examinations of B 4 C/stainless steel (s.s.) reaction couples obtained at temperatures of 1000, 1100 and 1200 C, and a theoretical model developed on the basis of these results, which describes the reaction layers growth kinetics, are presented. The examinations were carried out by AES and XMA methods to measure concentration profiles of different elements in the various phases and the thicknesses of the formed reaction layers as function of time to determine the growth kinetics. A new approach for modelling of diffusion mass transfer through a two-phase zone in multicomponent systems is further developed for the description of the growth kinetics of the reaction layer consisting of Me 2 B (Me≡Fe, Cr, Ni) precipitates in the stainless steel matrix. Diffusion coefficients of Cr in all phases of the reaction zone are calculated. These data together with the measured boundary concentrations of the elements allow the complete description of the B 4 C/s.s. interaction kinetics at the examined test temperatures by the proposed model. (orig.)

  5. Microstructural analysis of aluminum oxide boron carbide (Al2 O3-B4 C)

    International Nuclear Information System (INIS)

    Oliveira, E.E.M.; Bressiani, Ana H.A.; Bressiani, J.C.

    1996-01-01

    The densification Al 2 O 3 -B 4 C of composite was accomplished under two conditions: I- tungsten resistance furnace in commercial argon atmosphere without gas treatment system.II- graphite resistance furnace in argon atmosphere with gas treatment for humidity removal. The sintering with gas treatment showed higher density and smaller loss of mass for all composition related to the sintering in tungsten resistance furnace without gas treatment system. Microstructural characterization also showed that grain growth of alumina matrix is greatly influenced by particle size and concentration of B 4 C. Samples sintered at temperatures higher than 1750 deg C without gas treatment presented the formation of phase Al 3 B O 6 which was identified by transmission electron microscopy. (author)

  6. B4C control rod behavior during severe accident sequences

    International Nuclear Information System (INIS)

    Steinbrueck, M.

    2003-01-01

    The oxidation kinetics of various types of boron carbides (pellets, powder) as well as the degradation of B 4 C control rod segments were investigated in the temperature range between 800 and 1600 deg C. Mass spectrometric gas analysis was used to determine oxidation rates in transient and isothermal tests. The oxidation kinetics of boron carbide are determined by the formation of a liquid boron oxide layer and its loss due to the reaction with surplus steam to form volatile boric acids and at temperatures above 1500 deg C by direct evaporation. Under these test conditions linear oxidation kinetics are established soon after oxidation has initiated. The oxidation kinetics are strongly influenced by the thermal-hydraulic boundary conditions, in particular by the steam flow rate. Only very low amounts of methane were ever produced in these tests. Enhanced degradation of B 4 C control rods starts with the rapid formation of eutectic melts in the systems B 4 C-stainless steel (SS) and SS-Zircaloy at temperatures above 1250 deg C. Initially, this melt is kept within a ZrO 2 scale externally formed at the Zircaloy guide tube. The absorber melt is rapidly oxidized after failure of the oxide shell and aggressively attacks adjacent fuel claddings. (author)

  7. Pressure effect on structural, elastic, and thermodynamic properties of tetragonal B4C4

    Directory of Open Access Journals (Sweden)

    Baobing Zheng

    2015-03-01

    Full Text Available The compressibility, elastic anisotropy, and thermodynamic properties of the recently proposed tetragonal B4C4 (t-B4C4 are investigated under high temperature and high pressure by using of first-principles calculations method. The elastic constants, bulk modulus, shear modulus, Young’s modulus, Vickers hardness, Pugh’s modulus ratio, and Poisson’s ratio for t-B4C4 under various pressures are systematically explored, the obtained results indicate that t-B4C4 is a stiffer material. The elastic anisotropies of t-B4C4 are discussed in detail under pressure from 0 GPa to 100 GPa. The thermodynamic properties of t-B4C4, such as Debye temperature, heat capacity, and thermal expansion coefficient are investigated by the quasi-harmonic Debye model.

  8. Effects of B4C control rod degradation under severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Si-Won; Park, Sang-Gil; Han, Sang-Ku [Atomic Creative Technology Co., Daejeon (Korea, Republic of)

    2016-10-15

    Boron carbide (B4C) is widely used as absorber material in western boiling water reactor (BWR), some PWR, EPR and Russian RBMK and VVERs. B4C oxidation is one of the important phenomena of in-vessel. In the present paper, the main results and knowledge gained regarding the B4C control rod degradation from above mentioned experiments are reviewed and arranged to inform its significance on the severe accident consequences. In this paper, the role of B4C control rod oxidation and the subsequent degradation on the severe accident consequences is reviewed with available literature and report of previous experimental program regarding the B4C oxidation. From this review, it seems that the contribution of this B4C oxidation on the accident progression to the further severe accident situation is not negligible. For the future work, the extensive experimental data interpretation will be performed to assess quantitatively the effect of B4C oxidation and degradation on the various postulated severe accident conditions.

  9. Evaulation of B4C as an ablator material for NIF capsules. Revision 1

    International Nuclear Information System (INIS)

    Burnham, A.K.; Alford, C.S.; Makowiecki, D.M.; Dittrich, T.R.; Wallace, R.J.; Honea, E.C.; King, C.M.; Steinman, D.

    1997-01-01

    Boron carbide (B 4 C) is examined as a potential fuel container and ablator for implosion capsules on the National Ignition Facility (NIF). A capsule of pure B 4 C encasing a layer of solid DT implodes stably and ignites with anticipated NIF x-ray drives, producing 18 MJ of energy. Thin films of B 4 C were found to be resistant to oxidation and modestly transmitting in the infrared (IR), possibly enabling IR fuel characterization and enhancement for thin permeation barriers but not for full-thickness capsules. Polystyrene mandrels 0.5 mm in diameter were successfully coated with 0.15-2.0 micrometers of B 4 C. Thickness estimated from optical density agreed well with those measured by scanning electron microscopy (SEM). The B 4 C microstructure was columnar but finer than for Be made at the same conditions. B 4 C is a very strong material, with a fiber tensile strength capable of holding NIF fill pressures at room temperature, but it is also very brittle, and microscopic flaws or grain structure may limit the noncryogenic fill pressure. Argon (Ar) permeation rates were measured for a few capsules that had been further coated with 5 micrometers of plasma polymer. The B 4 C coatings tended to crack under tensile load. Some shells filled more slowly than they leaked, suggesting that the cracks open and close under opposite pressure loading. As observed earlier for Ti coatings, 0.15-micrometer layers of B 4 C had better gas retention properties than 2-micrometer layers, possibly because of fewer cracks. Permeation and fill strength issues for capsules with a full ablator thickness of B 4 C are unresolved. 21 refs., 6 figs

  10. Hot pressing of B4C/SiC composites

    International Nuclear Information System (INIS)

    Sahin, F.C.; Turhan, E.; Yesilcubuk, S.A.; Addemir, O.

    2005-01-01

    B 4 C/SiC ceramic composites containing 10-20-30 vol % SiC were prepared by hot pressing method. The effect of SiC addition and hot pressing temperature on sintering behaviour and mechanical properties of hot pressed composites were investigated. Microstructures of hot pressed samples were examined by SEM technique. Three different temperatures (2100 deg. C, 2200 deg. C and 2250 deg. C) were used to optimize hot pressing temperature applying 100 MPa pressure under argon atmosphere during the sintering procedure. The highest relative density of 98.44 % was obtained by hot pressing at 2250 deg. C. However, bending strengths of B 4 C/SiC composite samples were lower than monolithic B 4 C in all experimental conditions. (authors)

  11. Directional crystallization of B4C-NbB2 and B4C-MoB2 eutectic compositions

    International Nuclear Information System (INIS)

    Paderno, Varvara; Paderno, Y.B.; Filippov, Vladimir; Liashchenko, Alfred

    2004-01-01

    We studied the directional crystallization of different compositions in B 4 C-NbB 2 and B 4 C-MoB 2 systems. The eutectic compositions for both systems are evaluated. It is shown that in the first system the rod-like eutectic structure is formed, in second, the 'Chinese hieroglyphics'. In both cases high hardness and high microplasticity are observed, which are much more than for individual component phases. These compositions may be considered as a new kind of self-strengthening composite materials

  12. Gaseous swelling of B4C and UO2 fuel: similarities and differences

    International Nuclear Information System (INIS)

    Evdokimov, I.; Khoruzhii, O.; Kourtchatov, S.; Likhanskii, V.; Matweev, L.

    2001-01-01

    A major factor limiting the resource of control rods (CRs) for WWER-1000 reactors is their radiation damage. Radiation induced embrittlement of the CRs cladding, core swelling and gaseous internal pressure in CRs result in mechanical core-cladding interaction. This work is devoted to the physical analysis of processes that control the structural changes in neutron absorber elements with B 4 C under irradiation in water reactors. Particularly, the analysis of mechanisms of the helium porosity formation in B 4 C is undertaken. In view of the deficiency of experimental data on the subject, a fruitful approach to the problem is a comparative analysis of the swelling mechanisms in B 4 C absorber and UO 2 fuel. Using this similarity a phenomenological model of fission gas behavior in boron carbide is proposed. The model predictions for radial profile of 10 B burnup under influence of thermal and epithermal neutrons are compared with experimental results. The main results show that despite the external similarity of the process of fission gas accumulation in UO 2 and in B 4 C, phenomenology of gaseous swelling is much different for the fuel and the CR core. The reason for that difference is the distinction of physical conditions in irradiated fuel and CR core

  13. CODEX-B4C experiment. Core degradation test with boron carbide control rod

    International Nuclear Information System (INIS)

    Hozer, Z.; Nagy, I.; Windberg, P.; Balasko, M.; Matus, L.; Prokopiev, O.; Pinter, A.; Horvath, M.; Gyenes, Gy.; Czitrovszky, A.; Nagy, A.; Jani, P.

    2003-11-01

    The CODEX-B4C bundle test has been successfully performed on 25 th May 2001 in the framework of the COLOSS project of the EU 5 th FWP. The high temperature degradation of a VVER-1000 type bundle with B 4 C control rod was investigated with electrically heated fuel rods. The experiment was carried out according to a scenario selected in favour of methane formation. Degradation of control rod and fuel bundle took place at temperatures ∼2000 deg C, cooling down of the bundle was performed in steam atmosphere. The gas composition measurement indicated no methane production during the experiment. High release of aerosols was detected in the high temperature oxidation phase. The on-line measured data are collected into a database and are available for code validation and development. (author)

  14. Effect of the Ti/B4C mole ratio on the reaction products and reaction mechanism in an Al–Ti–B4C powder mixture

    International Nuclear Information System (INIS)

    Zhang, Jingjing; Lee, Jung-Moo; Cho, Young-Hee; Kim, Su-Hyeon; Yu, Huashun

    2014-01-01

    The effect of the Ti/B 4 C mole ratio on the fabrication behavior of Al composites is investigated using Al–Ti–B 4 C powder mixtures as reactants. The quick spontaneous infiltration (QSI) process combined with the combustion reaction and DTA analysis were used. According to the thermodynamic predictions, which are verified in the experimental results, TiB 2 is formed in all the samples whereas TiC is only formed in reactants with a Ti/B 4 C mole ratio of more than two. The C atoms from the reacted B 4 C do not move into TiC but instead they move into Al 3 BC or Al 4 C 3 when the Ti/B 4 C mole ratio is less than two. In addition, the reaction mechanism with a Ti/B 4 C mole ratio of 0.75 is investigated extensively. - Highlights: • The critical role of the Ti/B 4 C mole ratio on the reaction products of Al–Ti–B 4 C was studied using experiments. • The experimental results are also supported by thermodynamic calculations presented in this paper. • The reaction mechanism with a Ti/B 4 C mole ratio of 0.75 is investigated extensively

  15. Understanding micro-diffusion bonding from the fabrication of B4C/Ni composites

    Science.gov (United States)

    Wang, Miao; Wang, Wen-xian; Chen, Hong-sheng; Li, Yu-li

    2018-03-01

    A Ni-B4C macroscopic diffusion welding couple and a Ni-15wt%B4C composite fabricated by spark plasma sintering (SPS) were used to understand the micro-scale diffusion bonding between metals and ceramics. In the Ni-B4C macroscopic diffusion welding couple a perfect diffusion welding joint was achieved. In the Ni-15wt%B4C sample, microstructure analyses demonstrated that loose structures occurred around the B4C particles. Energy dispersive X-ray spectroscopy analyses revealed that during the SPS process, the process of diffusion bonding between Ni and B4C particles can be divided into three stages. By employing a nano-indentation test, the room-temperature fracture toughness of the Ni matrix was found to be higher than that of the interface. The micro-diffusion bonding between Ni and B4C particles is quite different from the Ni-B4C reaction couple.

  16. The effect of hydrogen on B4C coatings fabrication in inductively coupled plasma torch

    Directory of Open Access Journals (Sweden)

    Q. J. Guo

    2018-02-01

    Full Text Available Boron carbide (B4C coatings are prepared by an RF inductively coupled plasma (ICP torch with different amounts of hydrogen introduced into the sheath gas. The effects of the added hydrogen on the characteristics of the plasma are diagnosed by optical emission spectroscopy and high speed photography. The effects on the melting of B4C particles in the plasma are studied by scanning electron microscopy (SEM. The microstructure of the B4C coatings was determined with SEM imaging and x-ray diffraction analysis. The results show that adding hydrogen to the sheath gas leads to plasma contraction, which results in higher gas temperature of plasma. It also enhances B4C particles spheroidizing and improves the compactness of B4C coatings. Plasma processing does not change the main phase of boron carbide. The obtained results on B4C coatings on Cu substrates allows for improving the B4C coatings fabrication process.

  17. Peculiar features of metallurgical processes at plasma-arc spraying of coatings, made of steel wire with powder fillers B4C and B4C+ZrO2

    Directory of Open Access Journals (Sweden)

    Георгій Михайлович Григоренко

    2016-11-01

    Full Text Available The interaction of metallurgical processes occurring in plasma-arc spraying between the steel shell and the carbide fillers of B4C and B4C cored wires with the addition of nanocrystalline ZrO2 powder has been analyzed. Iron-boron compounds alloyed with carbon are formed in ingots as a result of ferritiс coating of wire interacrion with fillers while the ferritic matrix contains boride and carboboride eutectics. Average microhardness of the carboboride compounds and the matrix is high – 17,78; 16,40 and 8,69; 9,95 GPa for the ingots with с B4C and B4C+ZrO2 respectively. The best quality coatings with low porosity (~1%, lamellar structure consisting of ferrite matrix reinforced with dispersed Fe borides, were obtained at a higher heat input (plasmatron current 240-250 A. The average amount of oxides in the coatings makes 15%. 0,5% addition of nanopowder ZrO2 accelerates dispersed iron-boron compounds forming, promotes their uniform distribution in the structure and improves coating microhardness up to 7,0 GPa. Application of the differential thermal analysis method to simulate the interaction processes between the steel shell and the filler during the heating of wire in the shielding gas makes it possible to promote formation of new phases (borides and carboborides of iron and to predict the phase composition of the coatings

  18. CODEX-B4C experiment. Core degradation test with boron carbide control rod

    Energy Technology Data Exchange (ETDEWEB)

    Hozer, Z; Nagy, I; Windberg, P; Balasko, M; Matus, L; Prokopiev, O; Pinter, A; Horvath, M; Gyenes, Gy [KFKI Atomic Energy Research Institute, Budapest (Hungary); Czitrovszky, A; Nagy, A; Jani, P [Research Institute for Solid State Physics and Optics, Budapest (Hungary)

    2003-11-01

    The CODEX-B4C bundle test has been successfully performed on 25{sup th} May 2001 in the framework of the COLOSS project of the EU 5{sup th} FWP. The high temperature degradation of a VVER-1000 type bundle with B{sub 4}C control rod was investigated with electrically heated fuel rods. The experiment was carried out according to a scenario selected in favour of methane formation. Degradation of control rod and fuel bundle took place at temperatures {approx}2000 deg C, cooling down of the bundle was performed in steam atmosphere. The gas composition measurement indicated no methane production during the experiment. High release of aerosols was detected in the high temperature oxidation phase. The on-line measured data are collected into a database and are available for code validation and development. (author)

  19. Ceramic composite resistors of B4C modified by TIO2 and glass phase

    International Nuclear Information System (INIS)

    Klimiec, E.; Zaraska, W.; Stobiecki, T.

    1998-01-01

    Technical progress in the manufacturing technology of composite materials resulted in arising of new generation of bulk resistors, resistant to high levels of overloads and high temperature. These resistors can be applied in extremely heavy working conditions, for instance in cooperation with ignition circuits. The resistors investigated in our research were performed on the basis of ceramic composite consisted of semiconductor boron carbide B 4 C as conductive phase, aluminium oxide Al 2 O 3 and non-alkali glass as insulators and titanium dioxide TiO 2 . The technological procedure of the fabrication of resistors and the results of the tests, such as temperature dependence of the electrical resistance exploitation trials, are presented. (author)

  20. Effect of sintering temperature on structure of C-B4C-SiC composites with silicon additive

    International Nuclear Information System (INIS)

    Wu Lijun; Academia Sinica, Shenyang; Huang Qizhong; Yang Qiaoqin; Zhao Lihu; Xu Zhongyu

    1996-01-01

    Carbon materials possess good electric conductivity, heat conductivity, corrosion-resistance, self-lubrication and hot-shocking resistance, and are easily machined. However, they have low mechanical strength, and are easily oxidized in air at high temperature. On the contrary, ceramic materials have high mechanical strength and hardness, and have good wear-resistance and oxidation-resistance. However, they have the shortages of poor thermal-shock resistance lubrication, and are difficult to machine. Therefore, carbon/ceramic composites with the advantages of both carbon and ceramic materials have been widely studied in the recent years. Huang prepared C-B 4 C-SiC composites with the free sintering method and the hot pressing method, and studied the effects of Si, Al, Al 2 O 3 , Ni and Ti additives on the properties of the composites. The results showed that these additives could improve the properties of the composites. Zhao et al. studies the structure of C-B 4 C-SiC composites with Si additive sintered at 2,000 C and found two c-center monoclinic phases. In this paper, the authors discussed the effect of the sintering temperature on the structure of C-B 4 C-SiC composites with Si additive by means of transmission electron microscope (TEM) and x-ray diffractometer (XRD)

  1. Production and characterization of AA6061-B4C stir cast composite

    International Nuclear Information System (INIS)

    Kalaiselvan, K.; Murugan, N.; Parameswaran, Siva

    2011-01-01

    Highlights: → Stir casting of AA6061-B 4 C Composite. Color metallographic of composites → Enhanced wetting of B 4 C particles by K 2 TiF 6 flux. → Effect of B 4 C particles on mechanical properties of AA6061. -- Abstract: This work focuses on the fabrication of aluminum (6061-T6) matrix composites (AMCs) reinforced with various weight percentage of B 4 C particulates by modified stir casting route. The wettability of B 4 C particles in the matrix has been improved by adding K 2 TiF 6 flux into the melt. The microstructure and mechanical properties of the fabricated AMCs are analyzed. The optical microstructure and scanning electron microscope (SEM) images reveal the homogeneous dispersion of B 4 C particles in the matrix. The reinforcement dispersion has also been identified with X-ray diffraction (XRD). The mechanical properties like hardness and tensile strength have improved with the increase in weight percentage of B 4 C particulates in the aluminum matrix.

  2. Fine Structure Study of the Plasma Coatings B4C-Ni-P

    Science.gov (United States)

    Kornienko, E. E.; Bezrukova, V. A.; Kuz'min, V. I.; Lozhkin, V. S.; Tutunkova, M. K.

    2017-12-01

    The article considers structure of coatings formed of the B4C-Ni-P powder. The coatings were deposited using air-plasma spraying with the unit for annular injection of powder. The pipes from steel 20 (0.2 % C) were used as a substrate. The structure and phase composition of the coatings were studied by optical microscopy, scanning electron microscopy, transmission electron microscopy and X-ray diffractometry. It is shown that high-density composite coatings consisting of boron carbide particles distributed in the nickel boride metal matrix are formed using air-plasma spraying. The areas with round inclusions characterized by the increased amount of nickel, phosphorus and boron are located around the boron carbide particles. Boron oxides and nickel oxides are also present in the coatings. Thin interlayers with amorphous-crystalline structure are formed around the boron carbide particles. The thickness of these interlayers does not exceed 1 μm. The metal matrix material represents areas with nanocrystalline structure and columnar crystals.

  3. Al/ B4C Composites with 5 and 10 wt% Reinforcement Content Prepared by Powder Metallurgy

    International Nuclear Information System (INIS)

    Yusof Abdullah; Mohd Reusmaazran Yusof; Azali Muhammad; Nadira Kamarudin; Wilfred Sylvester Paulus; Roslinda Shamsudin; Nasrat Hannah Shudin; Nurazila Mat Zali

    2012-01-01

    The preparation, physical and mechanical properties of Al/ B 4 C composites with 5 and 10 wt.% reinforcement content were investigated. In order to obtain the feedstock with a low powder loading, B 4 C mixtures containing fine powders were investigated to obtain the optimal particle packing. The experimental results indicated that the fine containing 5 and 10 wt.% particles are able to prepare the feedstock with a good flowability. The composites fabricated by powder metallurgy have low densities and homogeneous microstructures. Additionally there is no interface reaction observed between the reinforcement and matrix by XRD analysis. The hardness of Al/ B 4 C composites prepared by powder metallurgy was high. (Author)

  4. Heterogeneous free-surface profile of B4C polycrystal under shock compression

    International Nuclear Information System (INIS)

    Mashimo, T.; Uchino, M.

    1997-01-01

    Observations of the free-surface behavior under shock compression by the gapped-flat mirror method were performed on B 4 C and Si 3 N 4 ceramics to study their shock-yielding properties. Jagged profiles of the moving free-surface in the plastic region, with a special scale of about one mm and a maximum local displacement of a few 10s of μm, were observed for B 4 C polycrystals. Similar profiles for Si 3 N 4 polycrystals were smooth. Such profiles for B 4 C polycrystals were also observed in the elastic region. It is suggested that these observations reflect the heterogeneous nature of shock compression in solids, and further indicate that a macroscopic slip system plays an important role in the elastoplastic transition of B 4 C material under shock compression and decompression. copyright 1997 American Institute of Physics

  5. Study of influence content of TiB2 by reaction in situ B4C and TiC in mechanical properties on B4C ceramics

    International Nuclear Information System (INIS)

    Coelho, M.L. Ramos; Bressiani, J.C.; Gomide, R.G.; Andrade, F.A. de

    2012-01-01

    The low density of ceramic materials promoted a change in research lines in the defense field. Research efforts and development directed to obtaining products of high density sintered of Al2O3, SiC and B4C, using different routes, both traditional as innovative, led to promising initial results, which justify the convergence of skills for the consolidation of research lines and the nationalization that sintered components of B4C with characteristics and properties compatible with the technical requirements established for the ballistic application. The low density of boron carbide (2.52 g/cm 3 ) gives in the final product a weight approximately 30% lower than armor made of alumina (3.96 g/cm 3 ). (author)

  6. Arcing at B4C-covered limiters exposed to a SOL-plasma

    International Nuclear Information System (INIS)

    Laux, M.; Schneider, W.; Wienhold, P.; Juettner, B.; Huber, A.; Balden, M.; Linke, J.; Kostial, H.; Mayer, M.; Rubel, M.; Herrmann, A.; Pospieszczyk, A.; Jachmich, S.; Schweer, B.; Hildebrandt, D.; Bolt, H.

    2003-01-01

    Plasma sprayed B 4 C-layers considered as wall coatings for the W7X stellarator have been studied during and after exposure to TEXTOR and after arcing experiments in vacuum. Arcing through the B 4 C layer occurred favoured by high power fluxes and not restricted to less stable phases. But this arcing implies an especially noisy scrape-off layer (SOL). Instead of moving retrograde in the external magnetic field, the arc spot on the B 4 C-layer sticks to the same location for its whole lifetime. Consequently, the arc erodes the entire B 4 C layer, finally burning down to the Cu substrate. In the neighbourhood of craters the surface contains Cu originating from those craters. This material, hauled to the surface by the arc, is subject to subsequent erosion, transport, and redeposition by the SOL-plasma. The behaviour of arcs on B 4 C is most probably caused by the peculiar temperature dependences of the electrical and heat conductivity of B 4 C

  7. Chemical interaction of B4C, B, and C with Mo/Si layered structures

    International Nuclear Information System (INIS)

    Rooij-Lohmann, V. I. T. A. de; Veldhuizen, L. W.; Zoethout, E.; Yakshin, A. E.; Kruijs, R. W. E. van de; Thijsse, B. J.; Gorgoi, M.; Schaefers, F.; Bijkerk, F.

    2010-01-01

    To enhance the thermal stability, B 4 C diffusion barrier layers are often added to Mo/Si multilayer structures for extreme ultraviolet optics. Knowledge about the chemical interaction between B 4 C and Mo or Si, however is largely lacking. Therefore, the chemical processes during annealing up to 600 deg. C of a Mo/B 4 C/Si layered structure have been investigated in situ with hard x-ray photoelectron spectroscopy and ex situ with depth profiling x-ray photoelectron spectroscopy. Mo/B/Si and Mo/C/Si structures have also been analyzed as reference systems. The chemical processes in these systems have been identified, with two stages being distinguished. In the first stage, B and C diffuse and react predominantly with Mo. MoSi x forms in the second stage. If the diffusion barrier consists of C or B 4 C, a compound forms that is stable up to the maximum probed temperature and annealing time. We suggest that the diffusion barrier function of B 4 C interlayers as reported in literature can be caused by the stability of the formed compound, rather than by the stability of B 4 C itself.

  8. Sintering of B4C powder obtained by a modified carbo-thermal reaction

    International Nuclear Information System (INIS)

    Rocha, R.M.; Kazumi, M.H.; Goncalves, D.P.; Melo, F.C.L.

    2005-01-01

    Boron carbide is one of the hardest materials and a highly refractory material that is of great interest for structural, electronic and nuclear applications. B 4 C is commercially manufactured by the carbo-thermal reduction of a mixture of boron oxide (B 2 O 3 ) in an batch electric arc furnace process. However the carbo-thermal reaction on the stoichiometric starting composition results an excess carbon residue because of the boron loss in the form of B 2 O 2 . Thus, a modified carbo-thermal reaction is applied with an excess B 2 O 3 to compensate the loss and to obtain stoichiometric powders. The aim of this work is to study the sinterability of this powder with the lower carbon residue acting as sintering additive. Pressureless sintering in the temperatures of 1900 deg. C/30 min and 2100 deg. C/30 min in argon atmosphere were applied. The synthesized powders were analysed by XRD and SEM. Density of 94% of theoretical density was achieved for sample prepared with the powder obtained with 50% B 2 O 3 excess synthesized at 1700 deg. C/15 min. (authors)

  9. Two-step infiltration of aluminum melts into Al-Ti-B4C-CuO powder mixture pellets

    Science.gov (United States)

    Zhang, Jingjing; Lee, Jung-Moo; Cho, Young-Hee; Kim, Su-Hyeon; Yu, Huashun

    2016-03-01

    Aluminum matrix composites with a high volume fraction of B4C and TiB2 were fabricated by a novel processing technique - a quick spontaneous infiltration process. The process combines a pressureless infiltration with the combustion reaction of Al-Ti-B4C-CuO in molten aluminum. The process is realized in a simple and economical way in which the whole process is performed in air in a few minutes. To verify the rapidity of the process, the infiltration kinetics was calculated based on the Washburn equation in which melt flows into a porous skeleton. However, there was a noticeable deviation from the calculated results with the experimental results. Considering the cross-sections of the samples at different processing times, a new infiltration model (two step infiltration) consisting of macro-infiltration and micro-infiltration is suggested. The calculated kinetics results in light of the proposed model agree well with the experimental results.

  10. Wetting of B4C, TiC and graphite substrates by molten Mg

    International Nuclear Information System (INIS)

    Zhang Dan; Shen Ping; Shi Laixin; Jiang Qichuan

    2011-01-01

    Highlights: → The wettability of TiC, B4C and C by molten Mg was determined using an improved sessile drop method. → A new method to evaluate the wetting behavior coupled with evaporation and reaction was proposed. → The bonding characteristics in the Mg/B4C, Mg/TiC and Mg/graphite systems were evaluated. - Abstract: The isotherm wetting of B 4 C, TiC and graphite substrates by molten Mg was studied in a flowing Ar atmosphere at 973-1173 K using an improved sessile drop method. The initial contact angles are in the ranges of 95-87 deg., 74-60 deg. and 142-124 deg., respectively, moderately depending on the temperature. All the systems are non-reactive in nature; however, the presence of impurity of free boron at the B 4 C surface gave rise to the chemical reaction with molten Mg and thus promoted the wettability to a certain degree. A new method was proposed to evaluate the wetting behavior coupled with evaporation and chemical reaction. Furthermore, based on the comparison of the work of adhesion and cohesion, the bonding in the Mg/B 4 C and Mg/TiC systems is presumably mainly chemical while that in the Mg/graphite system is physical.

  11. Interlayer growth in Mo/B4C multilayered structures upon thermal annealing

    International Nuclear Information System (INIS)

    Nyabero, S. L.; Kruijs, R. W. E. van de; Yakshin, A. E.; Zoethout, E.; Bosgra, J.; Loch, R. A.; Blanckenhagen, G. von; Bijkerk, F.

    2013-01-01

    Both multilayer period thickness expansion and compaction were observed in Mo/B 4 C multilayers upon annealing, and the physical causes for this were explored in detail. Using in situ time-dependent grazing incidence X-ray reflectometry, period changes down to picometer-scale were resolved. It was shown that the changes depend on the thickness of the B 4 C layers, annealing temperature, and annealing time. Although strong stress relaxation during annealing was observed, it was excluded as a cause for period expansion. Auger electron spectroscopy and wide angle X-ray diffraction measurements revealed the growth of interlayers, with associated period changes influenced by the supply of B and C atoms to the growing compound interlayers. For multilayers with a Mo thickness of 3 nm, two regimes were recognized, depending on the deposited B 4 C thickness: in multilayers with B 4 C ≤ 1.5 nm, the supply of additional Mo into the already formed MoB x C y interlayer was dominant and led to densification, resulting in period compaction. For multilayers with B 4 C ≥ 2 nm, the B and C enrichment of interlayers formed low density compounds and yielded period expansion.

  12. Wear behaviour of plasma-sprayed AlSi/B4C composite coatings

    International Nuclear Information System (INIS)

    Sarikaya, Ozkan; Anik, Selahaddin; Celik, Erdal; Okumus, S. Cem; Aslanlar, Salim

    2007-01-01

    This paper describes the wear behaviour of AlSi/B 4 C composite coatings with 0-25 wt% B 4 C particles for diesel engine motors. These coatings were successfully fabricated on AlSi substrates using an atmospheric plasma spray technique. The produced samples were characterized by means of an optical microscope, scanning electron microscope and microhardness tester. The obtained results pointed out that an increase of B 4 C particles in AlSi coatings was caused on the rising of the microhardness values and the decrease of the thermal expansion coefficient of the coatings. The friction and wear experiments were performed under dry conditions using a ball-on-dics configuration against WC/Co counter material for different loads. It was concluded that wear resistance of the coatings produced using B 4 C powders is greatly improved compared with the substrate material. The highest wear resistance of the coatings were also determined in the 20% B 4 C coating

  13. Enhancement of thermal neutron attenuation of nano-B4C, -BN dispersed neutron shielding polymer nanocomposites

    International Nuclear Information System (INIS)

    Kim, Jaewoo; Lee, Byung-Chul; Uhm, Young Rang; Miller, William H.

    2014-01-01

    Highlights: • Preparation of B 4 C and BN nanopowders using a simple ball milling process. • Homogeneous dispersion and strong adhesion of nano-B 4 C and -BN with polymer matrix. • Enhancement of mechanical properties of the nanocomposites compared to their micro counterparts. • Enhancement of thermal neutron attenuation of the nanocomposites. - Abstract: Nano-sized boron carbide (B 4 C) and boron nitride (BN) powder were prepared using ball milling. Micro- and milled nano-powders were melt blended with high density polyethylene (HDPE) using a polymer mixer followed by hot pressing to fabricate sheet composites. The tensile and flexural strengths of HDPE nanocomposites were ∼20% higher than their micro counterparts, while those for latter decreased compared to neat HDPE. Thermal neutrons attenuation of the prepared HDPE nanocomposites was evaluated using a monochromatic ∼0.025 eV neutron beam. Thermal neutron attenuation of the HDPE nanocomposites was greatly enhanced compared to their micro counterparts at the same B-10 areal densities. Monte Carlo n-Particles (MCNP) simulations based on the lattice structure modeling also shows the similar filler size dependent thermal neutron absorption

  14. Interface interaction in the B4C/(Fe-B-C) system

    International Nuclear Information System (INIS)

    Aizenshtein, M.; Mizrahi, I.; Froumin, N.; Hayun, S.; Dariel, M.P.; Frage, N.

    2008-01-01

    The wetting behavior in the B 4 C/(Fe-C-B) system was investigated in order to clarify the role of Fe additions on the sinterability of B 4 C. Iron and its alloys with C and B react with the boron carbide substrate and form a reaction zone consisting of a fine mixture of FeB and graphite. The apparent contact angles are relatively low for the alloys with a moderate concentration of the boron and carbon and allow liquid phase sintering to occur in the B 4 C-Fe mixtures. A dilatometric study of the sintering kinetics confirms that liquid phase sintering actually takes place and leads to improved mass transfer. A thermodynamic analysis of the ternary Fe-B-C system allows accounting for the experimental observations

  15. Effect of sintering temperature on the densification of B4C pellets

    International Nuclear Information System (INIS)

    Gomide, R.G.; Durazzo, M.; Riella, H.G.

    1990-01-01

    Boron is largely used in several types of nuclear reactors control and safety systems. In the majority of these applications sintered boron carbide pellets are used. Near stoichiometric B 4 C hardly densifies during pressureless sintering. As a starting point of an overall program to produce > 70% TD B 4 C pellets pressing parameters have been studied for further study of the influence of sintering temperature in the densification of this ceramic material. Dilatometric analyses show that sintering starts at 1760 0 C for the F 1200 ESK - type boron carbide powders. Moreover, the sintering experiments show that up to 92% TD pellets can be obtained. (author) [pt

  16. Application of full factorial design to study the tribological properties of AA6061-B4C and AA6061-B4C-MoS2 composites

    Directory of Open Access Journals (Sweden)

    Monikandan V. V.

    2018-03-01

    Full Text Available This study statistically analyzes the tribological properties of AA6061-10 wt. % B4C mono composite and AA6061-10 wt.% B4C-7.5 wt. % MoS2 hybrid composite. The tribological behavior of the composites was studied at atmospheric conditions using a pin-on-disk tribo-tester. The tribological experiments were conducted as per the full factorial design (FFD experimental scheme. The ANOVA analysis of the wear rate revealed that the three factors, A (MoS2 particles addition, B (applied load, and D (sliding distance presented the physical and statistical significance on the wear rate. The ANOVA analysis of the friction coefficient revealed that the factors B (applied load and C (sliding speed and interaction AB (interaction of MoS2 particles addition and applied load presented the physical and statistical significance on the friction coefficient. It is observed from the main effects plots of the wear rate and friction coefficient that the increase in the levels of factors B (applied load and D (sliding distance increased the wear rate and friction coefficient. However, the wear rate and friction coefficient decreased with the increase in the level of factor A (MoS2 particles addition.

  17. Microstructure and electrical properties of slug-type resistors based on B4C and TiC - ESCA - XPS and impedance spectroscopy investigations

    International Nuclear Information System (INIS)

    Klimiec, E.; Zaraska, W.; Stobiecki, T.; Bak, W.; Starzyk, F.

    2000-01-01

    The microstructure and electrical properties of slug-type resistors based on B 4 C and TiC were investigated. From XPS measurements was deducted that Ti in TiO 2 is in intermediate oxidation number between Ti +4 and Ti +3 . The impedance of both type of resistors is independent on frequency in the range from 10 3 to 10 4 Hz, only very subtle differences above 10 4 Hz are observed. The metallic type conductivity in TiC and semiconducting in B 4 C was established. (author)

  18. Nitridation and contrast of B4C/La interfaces and X-ray multilayer optics

    NARCIS (Netherlands)

    Tsarfati, T.; van de Kruijs, Robbert Wilhelmus Elisabeth; Zoethout, E.; Bijkerk, Frederik

    2010-01-01

    Chemical diffusion and interlayer formation in thin layers and at interfaces is of increasing influence in nanoscopic devices such as nano-electronics, magneto-optical storage and multilayer X-ray optics. We show that with the nitridation of reactive B4C/La interfaces, both the chemical and optical

  19. Grazing incidence Fe-line telescopes using W/B4C multilayers

    DEFF Research Database (Denmark)

    Joensen, K. D.; Gorenstein, P.; Christensen, Finn Erland

    1995-01-01

    The loss of throughput observed at higher energies for traditional grazing-incidence X-ray telescopes coated with high-Z elements can be partly countered by employing multilayers on the outermost reflectors. Using 8-keV reflectivity data from a periodic W/B4C multilayer, the expected performance...

  20. X-ray and EPR study of reactions between B4C and TiO2

    International Nuclear Information System (INIS)

    Kakazey, M.; Vlasova, M.; Gonzalez-Rodriguez, J.G.; Dominguez-Patino, M.; Leder, R.

    2006-01-01

    X-ray diffraction and electron paramagnetic resonance (EPR) methods have been used to study the reaction process in a system of 95 wt.% of B 4 C + 5 wt.% TiO 2 . The addition of TiO 2 to B 4 C was effective in accelerating the removal of carbon inclusions. Two types of reactions between B 4 C and TiO 2 , starting at temperatures ∼1173 K, took place: (a) gas-transport exchange and (b) diffusion of Ti atoms into the B 4 C lattice. These reactions modify the number and type of donor centers in the B 4 C. The dependence of EPR line width on the number of donor centers in B 4 C (from conditions of sample treatment) is a useful method for investigating the formation of powders and ceramics based on B 4 C

  1. Structural modifications induced by ion irradiation and temperature in boron carbide B4C

    Science.gov (United States)

    Victor, G.; Pipon, Y.; Bérerd, N.; Toulhoat, N.; Moncoffre, N.; Djourelov, N.; Miro, S.; Baillet, J.; Pradeilles, N.; Rapaud, O.; Maître, A.; Gosset, D.

    2015-12-01

    Already used as neutron absorber in the current French nuclear reactors, boron carbide (B4C) is also considered in the future Sodium Fast Reactors of the next generation (Gen IV). Due to severe irradiation conditions occurring in these reactors, it is of primary importance that this material presents a high structural resistance under irradiation, both in the ballistic and electronic damage regimes. Previous works have shown an important structural resistance of boron carbide even at high neutron fluences. Nevertheless, the structural modification mechanisms due to irradiation are not well understood. Therefore the aim of this paper is to study structural modifications induced in B4C samples in different damage regimes. The boron carbide pellets were shaped and sintered by using spark plasma sintering method. They were then irradiated in several conditions at room temperature or 800 °C, either by favoring the creation of ballistic damage (between 1 and 3 dpa), or by favoring the electronic excitations using 100 MeV swift iodine ions (Se ≈ 15 keV/nm). Ex situ micro-Raman spectroscopy and Doppler broadening of annihilation radiation technique with variable energy slow positrons were coupled to follow the evolution of the B4C structure under irradiation.

  2. Analysis of B4C influences on thermodynamic properties and phase separation of molten corium with ionic liquid U-Zr-Fe-O-B-C-FPs database

    International Nuclear Information System (INIS)

    Fukasawa, Masanori; Tamura, Shigeyuki; Saito, Masaki

    2009-01-01

    Boron carbide influences on thermodynamic properties and phase separation of molten corium such as liquidus temperature were estimated with our U-Zr-Fe-O-B-C-FPs thermodynamic database. The liquidus temperature of the oxide for the typical corium was estimated to increase by a hundred degrees with B 4 C addition when the corium included up to 10 wt% Fe. On the other hand, the liquidus temperature was hardly changed when the corium included 50 wt% Fe. The interaction temperature between the steel and the corium with B 4 C was estimated at 1130 K. We define the interaction temperature as the lowest temperature where the solid Fe and the liquid phase of a corium are in equilibrium, at which interactions such as microstructure change of the vessel were observed in test studies. Although it is 180 K lower than that without B 4 C, the estimated temperature is still over 200 K higher than the criterion temperature where the vessel loses its structural strength, which has been used in the feasibility evaluation of the in-vessel retention. Other thermodynamic influences of B 4 C were also estimated as not having a negative impact on the in-vessel retention. (author)

  3. Sputtering characteristics of B4C-overlaid graphite for keV energy deuterium ion irradiation

    International Nuclear Information System (INIS)

    Gotoh, Y.; Yamaki, T.; Ando, T.; Jimbou, R.; Ogiwara, N.; Saidoh, M.; Teruyama, K.

    1992-01-01

    Two types of B 4 C-overlaid graphite (CFC), conversion and CVD B 4 C, together with bare CFC (PCC-2S) and/or HP B 4 C, were investigated with respect to erosion yields for 1 keV D + , D 2 /CD 4 TDS after 1 keV D + implantation, and thermal diffusivity/conductivity, in a temperature range from 300 to 1400 K. The erosion yields of both conversion and CVD B 4 C were found to be much lower than that of the bare CFC (PCC-2S), in both chemical sputtering (600-1100 K) and RES (1200-1400 K) temperature regions. The D 2 TDS peak of the conversion B 4 C was found to be located at nearly 200 K lower temperature than that of the bare CFC (PCC-2S), indicating much lower activation energy for detrapping/recombination of trapped D in the conversion B 4 C and in the CFC. The CD 4 TDS peak of the conversion B 4 C was found to be much weaker in intensity than that of the bare CFC (PCC-2S), in agreement with the present erosion yield results. Thermal diffusivities and conductivities of both the conversion B 4 C/PCC-2S and the CVD B 4 C, were measured to be nearly 1/10 of that of the bare CFC (PCC-2S), and to decrease with increasing temperatures. (orig.)

  4. Characterization of B4C-composite-reinforced aluminum alloy composites

    Science.gov (United States)

    Singh, Ram; Rai, R. N.

    2018-04-01

    Dry sliding wear tests conducted on Pin-on-disk wear test machine. The rotational speed of disc is ranging from (400-600rpm) and under loads ranging from (30-70 N) the contact time between the disc and pin is constant for each pin specimen of composites is 15 minute. In all manufacturing industries the uses of composite materials has been increasing globally, In the present study, an aluminum 5083 alloy is used as the matrix and 5% of weight percentage of Boron Carbide (B4C) as the reinforcing material. The composite is produced using stir casting technique. This is cost effective method. The aluminum 5083 matrix can be strengthened by reinforcing with hard ceramic particles like silicon carbide and boron carbide. In this experiment, aluminum 5083 alloy is selected as one of main material for making parts of the ship it has good mechanical properties, good corrosion resistance and it is can welded very easily and does have good strength. The samples are tested for hardness and tensile strength. The mechanical properties like Hardness can be increased by reinforcing aluminum 5083alloy 5% boron carbide (B4C) particles and tensile strength. Finally the Scanning Electron Microscope (SEM) analysis and EDS is done, which helps to study topography of composites and it produces images of a sample by scanning it with a focused beam of electrons and the presence of composition found in the matrix.

  5. Optimization of laser cladding of cold spray coatings with B4C and Ni powders

    Science.gov (United States)

    Fomin, V. M.; Golyshev, A. A.; Malikov, A. G.; Orishich, A. M.; Filippov, A. A.; Ryashin, N. S.

    2017-12-01

    In the present work, a combined method is considered for the production of a metal-matrix composite coating based on Ni and B4C. The coating is created by consistently applied methods: cold spray and laser cladding. The conditions of obtaining cermet layers are investigated depending on the parameters of laser cladding and cold spray. It is shown that the laser track structure significantly changes in accordance to the size of ceramic particles ranging 3-75 µm and its concentration. It is shown that the most perspective layers for additive manufacturing could be obtain from cold spray coatings with ceramic concentrations more than 50% by weight treated in the heat-conductivity laser mode.

  6. B4C solid target boronization of the MST reversed-field pinch

    International Nuclear Information System (INIS)

    Den Hartog, D.J.; Cekic, M.; Fiksel, G.; Hokin, S.A.; Kendrick, R.D.; Prager, S.C.; Stoneking, M.R.

    1992-10-01

    A solid rod of hot-pressed boron carbide is being used as the source of boron during boronization of MST. The most striking result of this procedure is the reduction in oxygen contamination of the plasma (O III radiation, characteristic of oxygen at the edge, falls by about a factor of 3 after boronization.). The radiated power fraction drops to about half its initial value. Particle reflux from the wall is also lowered, making density control simpler. The rod (12.7 mm diameter) is inserted into the edge plasma of normal high-power RFP discharges. B 4 C is ablated from the surface of the rod and deposited in a thin film (a-B/C:H) on the walls and limiters. The energy flux carried by ''superthermal'' (not ''runaway'') electrons at the edge of MST appears to enhance the efficient, non-destructive ablation of the boron carbide rod

  7. Optical properties of boron carbide near the boron K edge evaluated by soft-x-ray reflectometry from a Ru/B4C multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Ksenzov, Dmitriy; Panzner, Tobias; Schlemper, Christoph; Morawe, Christian; Pietsch, Ullrich

    2009-12-10

    Soft-x-ray Bragg reflection from two Ru/B4C multilayers with 10 and 63 periods was used for independent determination of both real and imaginary parts of the refractive index n = 1 -{delta} + i{beta} close to the boron K edge ({approx}188 eV). Prior to soft x-ray measurements, the structural parameters of the multilayers were determined by x-ray reflectometry using hard x rays. For the 63-period sample, the optical properties based on the predictions made for elemental boron major deviations were found close to the K edge of boron for the 10-period sample explained by chemical bonding of boron to B4C and various boron oxides.

  8. Microstructural evolution and mechanical properties of Mg composites containing nano-B4C hybridized micro-Ti particulates

    International Nuclear Information System (INIS)

    Sankaranarayanan, S.; Sabat, R.K.; Jayalakshmi, S.; Suwas, S.; Gupta, M.

    2014-01-01

    In this work, the microstructural evolution and mechanical properties of extruded Mg composites containing micro-Ti particulates hybridized with varying contents of nano-B 4 C are investigated, and compared with Mg-5.6Ti. Microstructural characterization showed the presence of uniformly distributed micro-Ti particles embedded with nano-B 4 C particulates that resulted in significant grain refinement. Electron back scattered diffraction (EBSD) analyses of Mg-(5.6Ti + x-B 4 C) BM hybrid composites showed that the addition of hybridized particle resulted in relatively more recrystallized grains, realignment of basal planes and extension of weak basal fibre texture when compared to Mg-5.6Ti. The evaluation of mechanical properties indicated improved strength with ductility retention in Mg-(5.6Ti + x-B 4 C) BM hybrid composites. When compared to Mg-5.6Ti, the superior strength properties of the Mg-(5.6Ti + x-B 4 C) BM hybrid composites are attributed to the presence of nano-reinforcements, the uniform distribution of the hybridized particles, better interfacial bonding between the matrix and the reinforcement particles and the matrix grain refinement achieved by nano-B 4 C addition. The ductility enhancement obtained in hybrid composites can be attributed to the fibre texture spread and favourable basal plane orientation achieved due to nano B 4 C addition. - Highlights: • Micro-Ti particulates are hybridized with varying weight fractions of nano-B 4 C. • The hybrid mixture was used as hybrid reinforcements in magnesium. • Microstructure and mechanical properties of Mg-(5.6Ti + x-B 4 C) BM are compared with Mg-5.6Ti. • Electron back scattered diffraction (EBSD) analysis conducted to study the microtexture evolution

  9. Comparison of microstructural and mechanical properties of Al–TiC, Al–B4C and Al–TiC–B4C composites prepared by casting techniques

    International Nuclear Information System (INIS)

    Mazaheri, Y.; Meratian, M.; Emadi, R.; Najarian, A.R.

    2013-01-01

    In the present work, production of Al–10%TiC, Al–10% B 4 C, Al–5%TiC–5%B 4 C (volume fraction) composites by casting techniques were studied. However, casting techniques suffers from poor incorporation and distribution of the reinforcement particles in the matrix. These problems become especially significant as the reinforcement size decreases due to greater agglomeration tendency and reduced wettability of the particles with the melt. Microstructure characterization of the composite samples was investigated by using scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffractometer (XRD).The results showed heat treatment of B 4 C particles and addition of TiC particles with the flux improved the wettability and incorporation of reinforcement particles into melt. Mechanical characterization of samples showed that maximum hardness had belonged to Al–5%TiC–5%B 4 C composite, maximum yield and tensile strength had belonged to Al–10%B 4 C composite and maximum elongation had belonged to Al–10%TiC composite. Furthermore, wear properties of composites revealed the better behavior for Al–B 4 C composite.

  10. Analytical support for the B4C control rod test QUENCH-07

    International Nuclear Information System (INIS)

    Homann, C.; Hering, W.; Fernandez Benitez, J.A.; Ortega Bernardo, M.

    2003-04-01

    Degradation of B 4 C absorber rods during a beyond design accident in a nuclear power reactor may be a safety concern. Among others, the integral test QUENCH-07 is performed in the FZK QUENCH facility and supported by analytical work within the Euratom Fifth Framework Programme on Nuclear Fission Safety to get a more profound database. Since the test differed substantially from previous QUENCH tests, much more work had to be done for pretest calculations than usual to guarantee the safety of the facility and to derive the test protocol. Several institutions shared in this work with different computer code systems, as used for nuclear reactor safety analyses. Due to this effort, problems could be identified and solved, leading to several modifications of the originally planned test conduct, until a feasible test protocol could be derived and recommended. All calculations showed the same trends. Especially the high temperatures and hence the small safety margin for the facility were a concern. In this report, contributions of various authors, engaged in this work, are presented. The test QUENCH-07 and the related computational support by the engaged institutions were co-financed by the European Community under the Euratom Fifth Framework Programme on Nuclear Fission Safety 1998 - 2002 (COLOSS Project, contract No. FIKS-CT-1999-00002). (orig.)

  11. Wetting and interface interactions in the B4C/Al-Me (Me=Cu, Sn) systems

    International Nuclear Information System (INIS)

    Aizenshtein, M.; Froumin, N.; Dariel, M.P.; Frage, N.

    2008-01-01

    The wettability of B 4 C in contact with non-carbide and non-boride forming liquid metals (such as Cu or Sn) has been the subject of several studies. These metals do not wet boron carbide unless a reactive element is added to the melt. The present study is concerned with the addition of Al which completes the series of reactive elements added to the non-wetting metals. While Si represents the elements that form stable carbides and Ti represents the elements that form stable borides, Al belongs to the group of elements that form ternary borocarbides. The wetting experiments in the B 4 C/(Me-Al, Me=Cu, Sn) systems have shown that a ternary product, namely Al 8 B 4 C 7 was formed at the interface and that wetting is governed by the thermodynamic properties of the binary liquid system

  12. Spectral characterisation of aperiodic normal-incidence Sb/B4C multilayer mirrors for the λ < 124 Å range

    Science.gov (United States)

    Vishnyakov, E. A.; Kopylets, I. A.; Kondratenko, V. V.; Kolesnikov, A. O.; Pirozhkov, A. S.; Ragozin, E. N.; Shatokhin, A. N.

    2018-03-01

    Three broadband aperiodic Sb/B4C multilayer mirrors were synthesised for the purposes of soft X-ray optics and spectroscopy in the wavelength range beyond the L-edge of Si (λ plasma radiation source and an electronic detector with a 2D spatial resolution (a CCD matrix with 13 × 13 μm sized pixels). The experimental spectra are compared with theoretical calculations. The effect of lower antimony and B4C layer densities on the reflection spectra is discussed.

  13. Resonant soft x-ray reflectivity of Me/B4C multilayers near the boron K edge

    Energy Technology Data Exchange (ETDEWEB)

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich

    2010-09-01

    Energy dependence of the optical constants of boron carbide in the short period Ru/B4C and Mo/B4C multilayers (MLs) are evaluated from complete reflectivity scans across the boron K edge using the energy-resolved photon-in-photon-out method. Differences between the refractive indices of the B4Cmaterial inside and close to the surface are obtained from the peak profile of the first order ML Bragg peak and the reflection profile near the critical angle of total external reflection close to the surface. Where a Mo/B4C ML with narrow barrier layers appears as a homogeneous ML at all energies, a Ru/B4C ML exhibits another chemical nature of boron at the surface compared to the bulk. From evaluation of the critical angle of total external reflection in the energy range between 184 and 186 eV, we found an enriched concentration of metallic boron inside the Ru-rich layer at the surface, which is not visible in other energy ranges.

  14. Fabrication of steel matrix composites locally reinforced with different ratios of TiC/TiB2 particulates using SHS reactions of Ni-Ti-B4C and Ni-Ti-B4C-C systems during casting

    International Nuclear Information System (INIS)

    Yang Yafeng; Wang Huiyuan; Liang Yunhong; Zhao Ruyi; Jiang Qichuan

    2007-01-01

    Steel matrix composites locally reinforced with different molar ratios of in situ TiC/TiB 2 particulates (2:1, 1:1 and 1:2, respectively) have been fabricated successfully utilizing the self-propagating high-temperature synthesis (SHS) reactions of Ni-Ti-B 4 C and Ni-Ti-B 4 C-C systems during casting. Differential thermal analysis (DTA) and X-ray diffraction (XRD) results reveal that the exothermic reactions of the Ni-Ti-B 4 C and Ni-Ti-B 4 C-C systems proceed in such a way that Ni initially reacts with B 4 C and Ti to form Ni 2 B and Ti 2 Ni compounds, respectively, with heat evolution at 1037 deg. C; Subsequently, the external heat and the evolved heat from these exothermic reactions promote the reactions forming TiC and TiB 2 at 1133 deg. C. In the composites reinforced with 1:2 molar ratio of TiC/TiB 2 , almost all TiB 2 grains have clubbed structures, while TiC grains exhibit near-spherical morphologies. Furthermore, TiB 2 grain sizes decrease, with the increase of TiC content. In particular, in the composites reinforced with 2:1 molar ratio of TiC/TiB 2 , it is difficult to find the clubbed TiB 2 grains. Macro-pores and blowholes are absent in the local reinforcing region of the composites reinforced with 1:1 and 1:2 molar ratios of TiC/TiB 2 , while a few macro-pores can be observed in the composite reinforced with 2:1 molar ratio of TiC/TiB 2 . Moreover, the densities of the composites reinforced with 1:1 and 1:2 molar ratios of TiC/TiB 2 are higher than that of the composite reinforced with 2:1 molar ratio of TiC/TiB 2 . The composite reinforced with 1:2 molar ratio of TiC/TiB 2 has the highest hardness and the best wear resistance

  15. Mechanical performance optimization of neutron shielding material based on short carbon fiber reinforced B4C/epoxy resin

    International Nuclear Information System (INIS)

    Wang Peng; Tang Xiaobin; Chen Feida; Chen Da

    2013-01-01

    To satisfy engineering requirements for mechanics performance of neutron shielding material, short carbon fiber was used to reinforce the traditional containing B 4 C neutron shielding material and effects of fiber content, length and surface treatment to mechanics performance of material was discussed. Based on Americium-Beryllium neutron source, material's neutron shielding performance was tested. The result of experiment prove that tensile strength of material which the quality ratio of resin and fiber is 5:1 is comparatively excellent for 10wt% B 4 C of carbon fiber reinforced epoxy resin. The tensile properties of material change little with the fiber length ranged from 3-10 mm The treatment of fiber surface with silane coupling agent KH-550 can increase the tensile properties of materials by 20% compared with the untreated of that. A result of shielding experiment that the novel neutron shielding material can satisfy the neutron shielding requirements can be obtained by comparing with B 4 C/polypropylene materials. The material has good mechanical properties and wide application prospect. (authors)

  16. A comparison study on the densification behavior and mechanical properties of gelcast vs conventionally formed B4C sintered conventionally and by microwaves

    International Nuclear Information System (INIS)

    Menchhofer, P.A.; Kiggans, J.O.; Morrow, M.S.; Schechter, D.E.

    1996-01-01

    The utilization of microwave energy for reaching high temperatures necessary to densify B 4 C powder is compared with conventional means of sintering by evaluating the mechanical properties after densification. Microwave energy has been shown to be an effective means for achieving high sintered densities, even though temperatures of ∼ 2,250 C are required. In this study, green preforms of B 4 C specimens were sintered by both conventional and microwave heating. This study also utilized an advanced forming method called ''Gelcasting'' developed at ORNL. Gelcasting is a fluid forming process whereby high solids suspensions of powders containing dissolved monomers are cast into a mold, then polymerized or ''gelled'' in situ. This investigation compares microstructures and mechanical properties of both Gelcast B 4 C and ''conventionally'' die-pressed B 4 C. The microstructures and final mechanical properties of B 4 C specimens are discussed

  17. Processing and characterization of laser sintered hybrid B4C/cBN reinforced Ti-based metal matrix composite

    Science.gov (United States)

    Gupta, Ankit; Hussain, Manowar; Misra, Saurav; Das, Alok Kumar; Mandal, Amitava

    2018-06-01

    The purpose of this study is to make a boron carbide (B4C) and cubic boron nitride (cBN) reinforced Ti6Al4V metal matrix composites (MMC's) by direct metal laser sintering (DMLS) technique using the continuous wave (CW) SPI fiber laser and to check the feasibility of the formation of three dimensional objects by this process. For this study, the process parameters like laser power density (3.528-5.172 W/cm2 (×104), scanning speed (3500-4500 mm/min), composition of the reinforced materials B4C (5-25% by volume) and cBN (3% by volume) were taken as input variables and hatching gap (0.2 mm), spot diameter (0.4 mm), layer thickness (0.4 mm) were taken as constant. It was analyzed that surface characteristic, density and the mechanical properties of sintered samples were greatly influenced by varying the input process parameters. Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDX) and X-Ray diffraction (XRD) were performed for microstructural analysis, elemental analysis, and recognition of intermetallic compounds respectively. Mechanical properties like micro-hardness & wear rate were examined by Vickers micro-hardness tester & pin on disc arrangement respectively. From hardness tests, it was observed that hardness property of the sintered specimens was increased as compared to the parent material. The XRD results show that there is a good affinity between Ti6Al4V-B4C-cBN to produce various intermetallic compounds which themselves enhance the mechanical properties of the samples. From FESEM analysis, we can conclude that there is a uniform distribution of reinforcements in the titanium alloy matrix. Furthermore, the coefficient of friction (COF) was characterized by the irregular pattern and it tends to decrease with an increase in the volume % of reinforcement. The results obtained in this work may be useful in preparing the MMC's with improved mechanical properties and overall characteristics.

  18. Specially designed B4C/SnO2 nanocomposite for photocatalysis: traditional ceramic with unique properties

    Science.gov (United States)

    Singh, Paviter; Kaur, Gurpreet; Singh, Kulwinder; Singh, Bikramjeet; Kaur, Manpreet; Kaur, Manjot; Krishnan, Unni; Kumar, Manjeet; Bala, Rajni; Kumar, Akshay

    2018-02-01

    Boron carbide: A traditional ceramic material shows unique properties when explored in nano-range. Specially designed boron-based nanocomposite has been synthesized by reflux method. The addition of SnO2 in base matrix increases the defect states in boron carbide and shows unique catalytic properties. The calculated texture coefficient and Nelson-Riley factor show that the synthesized nanocomposite has large number of defect states. Also this composite is explored for the first time for catalysis degradation of industrial used dyes. The degradation analysis of industrial pollutants such as Novacron red Huntsman (NRH) and methylene blue (MB) dye reveals that the composite is an efficient catalyst. Degradation study shows that 1 g/L catalyst concentration of B4C/SnO2 degrades NRH and MB dye up to approximately 97.38 and 79.41%, respectively, in 20 min under sunlight irradiation. This water-insoluble catalyst can be recovered and reused.

  19. Reactivity and neutron flux measurements in IPEN/MB-01 reactor with B4C burnable poison

    International Nuclear Information System (INIS)

    Fer, Nelson Custodio; Moreira, Joao Manoel Losada

    2000-01-01

    Burnable poison rods, made of B 4 C- Al 2 O 3 pellets with 5.01 mg/cm 3 10 B concentration, have been manufactured for a set of experiments in the IPEN/MB-01 zero-power reactor. Several core parameters which are affected by the burnable poisons rods have been measured. The principal results, for the situation in which the burnable poison rods are located near the absorber rods of a control rod, are they cause a 29% rod worth shadowing, a reduction of 39% in the local void coefficient of reactivity, a reduction of 4.8% in the isothermal temperature coefficient of reactivity, and a reduction of 9% in the thermal neutron flux in the region where the burnable poison rods are located. These experimental results will be used for the validation of burnable poison calculation methods in the CTMSP. (author)

  20. First-principles investigation of neutron-irradiation-induced point defects in B4C, a neutron absorber for sodium-cooled fast nuclear reactors

    Science.gov (United States)

    You, Yan; Yoshida, Katsumi; Yano, Toyohiko

    2018-05-01

    Boron carbide (B4C) is a leading candidate neutron absorber material for sodium-cooled fast nuclear reactors owing to its excellent neutron-capture capability. The formation and migration energies of the neutron-irradiation-induced defects, including vacancies, neutron-capture reaction products, and knocked-out atoms were studied by density functional theory calculations. The vacancy-type defects tend to migrate to the C–B–C chains of B4C, which indicates that the icosahedral cage structures of B4C have strong resistance to neutron irradiation. We found that lithium and helium atoms had significantly lower migration barriers along the rhombohedral (111) plane of B4C than perpendicular to this plane. This implies that the helium and lithium interstitials tended to follow a two-dimensional diffusion regime in B4C at low temperatures which explains the formation of flat disk like helium bubbles experimentally observed in B4C pellets after neutron irradiation. The knocked-out atoms are considered to be annihilated by the recombination of the close pairs of self-interstitials and vacancies.

  1. Characterization of Carbon-Contaminated B4C-Coated Optics after Chemically Selective Cleaning with Low-Pressure RF Plasma.

    Science.gov (United States)

    Moreno Fernández, H; Rogler, D; Sauthier, G; Thomasset, M; Dietsch, R; Carlino, V; Pellegrin, E

    2018-01-22

    Boron carbide (B 4 C) is one of the few materials that is expected to be most resilient with respect to the extremely high brilliance of the photon beam generated by free electron lasers (FELs) and is thus of considerable interest for optical applications in this field. However, as in the case of many other optics operated at light source facilities, B 4 C-coated optics are subject to ubiquitous carbon contaminations. Carbon contaminations represent a serious issue for the operation of FEL beamlines due to severe reduction of photon flux, beam coherence, creation of destructive interference, and scattering losses. A variety of B 4 C cleaning technologies were developed at different laboratories with varying success. We present a study regarding the low-pressure RF plasma cleaning of carbon contaminated B 4 C test samples via inductively coupled O 2 /Ar, H 2 /Ar, and pure O 2 RF plasma produced following previous studies using the same ibss GV10x downstream plasma source. Results regarding the chemistry, morphology as well as other aspects of the B 4 C optical coating before and after the plasma cleaning are reported. We conclude that among the above plasma processes only plasma based on pure O 2 feedstock gas exhibits the required chemical selectivity for maintaining the integrity of the B 4 C optical coatings.

  2. TiO2 nanosheets decorated with B4C nanoparticles as photocatalysts for solar fuel production under visible light irradiation

    Science.gov (United States)

    Zhang, Xiaojie; Yang, Jipeng; Cai, Tiancong; Zuo, Guoqiang; Tang, Changqing

    2018-06-01

    Boron carbide (B4C) nanoparticles-decorated anatase titanium dioxide (TiO2) nanosheets photocatalysts were synthesized by a hydrothermal method in the presence of hydrofluoric acid and characterized by field emission scanning electron microscope, high-resolution transmission electron microscope, UV-vis diffuse reflectance spectra, photoluminescence spectra, etc. With metallic Pt nanoparticles as a co-catalyst, the as-synthesized B4C/TiO2 composites were evaluated using photocatalytic CO2 or H2O reduction to solar fuels such as methane and hydrogen. Under either simulated sunlight or visible light irradiation, coupling p-type B4C with n-type anatase TiO2 significantly improved the photocatalytic performance. Both photoluminescence and transient photocurrent measurements indicated that the interfacial coupling effect between B4C and anatase TiO2 could significantly promote photo-excited charges separations. On the basis of measurements and literatures, a possible mechanism of excited charges transfer at the B4C-anatase TiO2 heterojunction interface during irradiation was deduced.

  3. Enhancement in the microstructure and neutron shielding efficiency of sandwich type of 6061Al–B4C composite material via hot isostatic pressing

    International Nuclear Information System (INIS)

    Park, Jin-Ju; Hong, Sung-Mo; Lee, Min-Ku; Rhee, Chang-Kyu; Rhee, Won-Hyuk

    2015-01-01

    Highlights: • 6061Al–B 4 C neutron shielding composites are fabricated by sintering and HIP. • HIP process improves the wettability of B 4 C particles into 6061Al matrix. • Neutron attenuation performance can be enhanced by application of HIP process. - Abstract: Sandwich type of 6061Al–B 4 C composite plates, which are used as a thermal neutron absorber for spent nuclear fuel pool storage rack, were fabricated using two different consolidation ways as sintering and hot isostatic pressing (HIP) processes and their thermal neutron shielding efficiency was investigated as a function of B 4 C concentration ranging from 0 to 40 wt.%. For this purpose, two respective inner core compaction parts of sintered and HIPped neutron absorbing composite materials were first produced and then cladded them between two outer plates by HIP process. The application of HIP process provided not only a lead of excellent interfacial adhesion due to the improved wettability but also an enhancement of thermal neutron shielding efficiency owing to the more uniform dispersion of B 4 C particles

  4. Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

    Science.gov (United States)

    Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

    2017-10-01

    The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

  5. Optimization of friction and wear behaviour of Al7075-Al2O3-B4C metal matrix composites using Taguchi method

    Science.gov (United States)

    Dhanalakshmi, S.; Mohanasundararaju, N.; Venkatakrishnan, P. G.; Karthik, V.

    2018-02-01

    The present study deals with investigations relating to dry sliding wear behaviour of the Al 7075 alloy, reinforced with Al2O3 and B4C. The hybrid composites are produced through Liquid Metallurgy route - Stir casting method. The amount of Al2O3 particles is varied as 3, 6, 9, 12 and 15 wt% and the amount of B4C is kept constant as 3wt%. Experiments were conducted based on the plan of experiments generated through Taguchi’s technique. A L27 Orthogonal array was selected for analysis of the data. The investigation is to find the effect of applied load, sliding speed and sliding distance on wear rate and Coefficient of Friction (COF) of the hybrid Al7075- Al2O3-B4C composite and to determine the optimal parameters for obtaining minimum wear rate. The samples were examined using scanning electronic microscopy after wear testing and analyzed.

  6. Influence of B4C-doping and high-energy ball milling on phase formation and critical current density of (Bi,Pb)-2223 HTS

    Science.gov (United States)

    Margiani, N. G.; Mumladze, G. A.; Adamia, Z. A.; Kuzanyan, A. S.; Zhghamadze, V. V.

    2018-05-01

    In this paper, the combined effects of B4C-doping and planetary ball milling on the phase evolution, microstructure and transport properties of Bi1.7Pb0.3Sr2Ca2Cu3Oy(B4C)x HTS with x = 0 ÷ 0.125 were studied through X-ray diffraction (XRD), scanning electron microscopy (SEM), resistivity and critical current density measurements. Obtained results have shown that B4C additive leads to the strong acceleration of high-Tc phase formation and substantial enhancement in Jc. High-energy ball milling seems to produce a more homogeneous distribution of refined doped particles in the (Bi,Pb)-2223 HTS which results in an improved intergranular flux pinning and better self-field Jc performance.

  7. Effects of B4C Addition on the Laser Beam Welding Characteristics of Al/SiC MMCs Produced By P/M

    Directory of Open Access Journals (Sweden)

    Serdar KARAOĞLU

    2011-01-01

    Full Text Available Fusion weldability characteristics of metal matrix composites (MMC produced by powder metallurgy (P/M are usually insufficient due to unwanted micro-structural changes that occur during welding. This study aims to investigate the effects of B4C addition as reinforcement on the weld quality of Al/SiC MMCs. After the production of Al/SiC MMCs by P/M with or without the addition of B4C, laser beam welding (LBW characteristics of the materials were investigated by focusing on the integrity of the welds. Optical microscopy (OM, scanning electron microscopy (SEM, and energy dispersive X-ray analysis (EDX were utilized for the characterization of the welds. Results show that Al/SiC MMCs produced by P/M can not be easily welded by LBW, but weldability characteristics of the material can be improved by the addition of B4C.

  8. Preparation and characteristics of epoxy/clay/B4C nanocomposite at high concentration of boron carbide for neutron shielding application

    Science.gov (United States)

    Kiani, Mohammad Amin; Ahmadi, Seyed Javad; Outokesh, Mohammad; Adeli, Ruhollah; Mohammadi, Aghil

    2017-12-01

    In this research, the characteristics of the prepared samples in epoxy matrix by means of X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), as well as scanning electron microscope (SEM) are evaluated. Meanwhile, the obtained mechanical properties of the specimen are investigated. Thermogravimetric analysis (TGA) is also employed to evaluate the thermal degradation of manufactured nanocomposites. The thermal neutron absorption properties of nanocomposites containing 3 wt% of montmorillonite nanoclay (closite30B) have been studied experimentally, using an Am-Be point source. Mechanical tests reveal that the higher B4C concentrations, the more tensile strengths, but lower Young's modulus in all samples under consideration. TGA analysis also shows that thermal stability of the nanocomposite, increases in presence of B4C. Finally, neutron absorption analysis shows that increasing the B4C concentration leads to a nonlinearly build-up of neutron absorption cross section.

  9. Friction Stir Welding of Al-B4C Composite Fabricated by Accumulative Roll Bonding: Evaluation of Microstructure and Mechanical Behavior

    Science.gov (United States)

    Moradi Faradonbeh, Alireza; Shamanian, Morteza; Edris, Hossein; Paidar, Moslem; Bozkurt, Yahya

    2018-02-01

    In this investigation, friction stir welding (FSW) of Al-B4C composite fabricated by 10 cycles accumulative roll bonding was conducted. In order to investigate the influences of pin geometry on microstructure and mechanical properties, four different pin geometries (cylindrical, square, triangular and hexagonal) were selected. It was found that FSW parameters had a major effect on the fragmentation and distribution of reinforcement particles in stir zone. When the tool travel speed was increased, the distribution of B4C particles was become gradually uniform in the aluminum matrix. The effect of tool rotational speed on the peak temperature was determined to be greater than the tool travel speed. The attained data of tensile properties and microhardness tests showed that the tool travel speed had bilateral effect on the tensile strength. The maximum tensile joint efficiency was obtained as 238% for FSWed of Al-2%B4C composite to annealed base Al sheet.

  10. The effect of strontium on the microstructure, porosity and tensile properties of A356-10%B4C cast composite

    International Nuclear Information System (INIS)

    Lashgari, H.R.; Emamy, M.; Razaghian, A.; Najimi, A.A.

    2009-01-01

    This study was undertaken to investigate the effect of different concentrations of strontium (0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 1%) on the microstructure, porosity content and tensile properties of A356-10%B 4 C particulate metal matrix composite. In this work, the matrix alloy and composite were characterized by optical microscope, scanning electron microscope equipped with EDS and XRD. The composite ingots were made by stir casting process. The results showed that the addition of 0.03%Sr strongly modified silicon eutectic phase in A356 monolithic alloy, but 0.5%Sr was needed to complete the modification of A356-10%B 4 C composite. Results also demonstrated that Sr addition increases shrinkage porosity and generates new intermetallics in the microstructure. Further investigations on tensile tests revealed optimum strontium levels for improving tensile properties. In the point of fracture behavior of the composite, modified specimens with 0.2%Sr showed broken B 4 C particles and acceptable cohesion between B 4 C and matrix.

  11. Heat treatment effect on the microstructure, tensile properties and dry sliding wear behavior of A356-10%B4C cast composites

    International Nuclear Information System (INIS)

    Lashgari, H.R.; Zangeneh, Sh.; Shahmir, H.; Saghafi, M.; Emamy, M.

    2010-01-01

    In present paper, an attempt was made to examine the influence of T6 heat treatment (solution treatment at 540 o C for 5 h, quenching in hot water and artificial aging at 170 o C for 8 h) on the microstructure, tensile properties and dry sliding wear behavior of A356-10%B 4 C cast composites. The composite ingots were made by stir casting process. In this work, the matrix alloy and composite were characterized by optical microscope, scanning electron microscope equipped with energy dispersive X-ray spectroscopy, tensile tests and conventional pin-on-disk experiment. The obtained results showed that in Al-B 4 C composite, T6 treatment was a dominant factor on the hardness improvement in comparison with hardness increasing due to the addition of B 4 C hard particles. In addition, T6 treatment can contribute to the strong bonding between B 4 C and matrix alloy and also it can change eutectic silicon morphology from acicular to near spherical. This case can lead to higher strength and wear properties of heat treated metal matrix composites in comparison with unheat treated state. Observation of worn surfaces indicated detachment of mechanically mixed layer which can primarily due to the delamination wear mechanism under higher applied load.

  12. Dry sliding tribological behavior and mechanical properties of Al2024–5 wt.%B4C nanocomposite produced by mechanical milling and hot extrusion

    International Nuclear Information System (INIS)

    Abdollahi, Alireza; Alizadeh, Ali; Baharvandi, Hamid Reza

    2014-01-01

    Highlights: • Nanostructured Al2024 and Al2024–B 4 C nanocomposite prepared via mechanical milling. • The milled powders formed by hot pressing and then exposed to hot extrusion. • Tribological behavior and mechanical properties of samples were investigated. • Al2024–B 4 C nanocomposite showed a better wear resistance and mechanical properties. - Abstract: In this paper, tribological behavior and mechanical properties of nanostructured Al2024 alloy produced by mechanical milling and hot extrusion were investigated before and after adding B 4 C particles. Mechanical milling was used to synthesize the nanostructured Al2024 in attrition mill under argon atmosphere up to 50 h. A similar process was used to produce Al2024–5 wt.%B 4 C composite powder. The milled powders were formed by hot pressing and then were exposed to hot extrusion in 750 °C with extrusion ratio of 10:1. To study the microstructure of milled powders and hot extruded samples, optical microscopy, transmission electron microscopy and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectrometer (EDS) were used. The mechanical properties of samples were also compared together using tension, compression and hardness tests. The wear properties of samples were studied using pin-on-disk apparatus under a 20 N load. The results show that mechanical milling decreases the size of aluminum matrix grains to less than 100 nm. The results of mechanical and wear tests also indicate that mechanical milling and adding B 4 C particles increase strength, hardness and wear resistance of Al2024 and decrease its ductility remarkably

  13. Laser cladding Ni-base composite coating on titanium alloy with pre-placed B4C+NiCoCrAlY

    International Nuclear Information System (INIS)

    Qingwu Meng; Lin Geng; Zhenzhu Zheng

    2005-01-01

    Using a CO 2 laser, a process of cladding Ni-base composite coating on Ti6Al4V with pre-placed B 4 C and NiCoCrAlY was studied. A good metallurgical bonding coating without cracks and pores was obtained in reasonable ratio of components and low energy laser process. Morphology and microstructure of the coating were analyzed with OM, XRD, SEM and EDS. It is certain that there was a reaction between B 4 C and Ti during in-situ producing TiB 2 and TiC. The Ni-base composite coating is strengthened with TiB 2 and TiC reinforcement phases. Vickers hardness tester measured that the average microhardness of the coating is HV1200 and it is 3.5 times of the Ti6Al4V substrate. The high hard coating containing several reinforcement phases greatly enhances wear resistance of titanium alloy. (orig.)

  14. Investigation of the microstructure of Ni and B4C ceramic-metal mixtures obtained by cold spray coating and followed by laser cladding

    Science.gov (United States)

    Filippov, A. A.; Fomin, V. M.; Orishich, A. M.; Malikov, A. G.; Ryashin, N. S.; Golyshev, A. A.

    2017-10-01

    In the present work, a combined method is considered for the production of a metal-matrix composite coating based on Ni and B4C. The coating is created by consistently applied methods: cold spray and laser cladding. Main focus of this work aimed to microstructure of coatings, element content and morphology of laser tracks. At this stage, the authors focused on the interaction of the laser unit with the substance without affecting the layer-growing technology products. It is shown that coating has deformed particles of nickel and the significantly decreased content of ceramic particles B4C after cold spray. After laser cladding there are no boundaries between nickel and dramatically changes in ceramic particles.

  15. A Tri-modal 2024 Al -B4C composites with super-high strength and ductility: Effect of coarse-grained aluminum fraction on mechanical behavior

    Directory of Open Access Journals (Sweden)

    Alireza Abdollahi

    2014-12-01

    Full Text Available In this study, ultrafine grained 2024 Al alloy based B4C particles reinforced composite was produced by mechanical milling and hot extrusion. Mechanical milling was used to synthesize the nanostructured Al2024 in attrition mill under argon atmosphere up to 50h. A similar process was used to produce Al2024-5%wt. B4C composite powder. To produce trimodal composites, milled powders were combined with coarse grained aluminum in 30 and 50 wt% and then were exposed to hot extrusion at 570°C. The microstructure of hot extruded samples were studied by optical microscope, Transmission electron microscope (TEM and scanning electron microscope (SEM equipped with EDS spectroscopy. The mechanical properties of samples were compared by using tensile, compression and hardness tests. The results showed that the strength, after 50 h milling and addition of 5wt% B4C, increased from 340 to 582 MPa and the hardness increased from 87 HBN to 173 HBN, but the elongation decreased from 14 to 0.5%. By adding the coarse-grained aluminum powder, the strength and hardness decreased slightly, but the increases in return. Ductility increase is the result of increase in dislocation movements and strength increase is the result of restriction in plastic deformation by nanostructured regions. Furthermore, the strength and hardness of trimodal composites were higher, but their ductility was lower.

  16. Measurements and Monte-Carlo simulations of the particle self-shielding effect of B4C grains in neutron shielding concrete

    Science.gov (United States)

    DiJulio, D. D.; Cooper-Jensen, C. P.; Llamas-Jansa, I.; Kazi, S.; Bentley, P. M.

    2018-06-01

    A combined measurement and Monte-Carlo simulation study was carried out in order to characterize the particle self-shielding effect of B4C grains in neutron shielding concrete. Several batches of a specialized neutron shielding concrete, with varying B4C grain sizes, were exposed to a 2 Å neutron beam at the R2D2 test beamline at the Institute for Energy Technology located in Kjeller, Norway. The direct and scattered neutrons were detected with a neutron detector placed behind the concrete blocks and the results were compared to Geant4 simulations. The particle self-shielding effect was included in the Geant4 simulations by calculating effective neutron cross-sections during the Monte-Carlo simulation process. It is shown that this method well reproduces the measured results. Our results show that shielding calculations for low-energy neutrons using such materials would lead to an underestimate of the shielding required for a certain design scenario if the particle self-shielding effect is not included in the calculations.

  17. Effect of Cutting Parameters on Thrust Force and Surface Roughness in Drilling of Al-2219/B4C/Gr Metal Matrix Composites

    Science.gov (United States)

    Ravindranath, V. M.; Basavarajappa, G. S. Shiva Shankar S.; Suresh, R.

    2016-09-01

    In aluminium matrix composites, reinforcement of hard ceramic particle present inside the matrix which causes tool wear, high cutting forces and poor surface finish during machining. This paper focuses on effect of cutting parameters on thrust force, surface roughness and burr height during drilling of MMCs. In the present work, discuss the influence of spindle speed and feed rate on drilling the pure base alloy (Al-2219), mono composite (Al- 2219+8% B4C) and hybrid composite (Al-2219+8%B4C+3%Gr). The composites were fabricated using liquid metallurgy route. The drilling experiments were conducted by CNC machine with TiN coated HSS tool, M42 (Cobalt grade) and carbide tools at various spindle speeds and feed rates. The thrust force, surface roughness and burr height of the drilled hole were investigated in mono composite and hybrid composite containing graphite particles, the experimental results show that the feed rate has more influence on thrust force and surface roughness. Lesser thrust force and discontinuous chips were produced during machining of hybrid composites when compared with mono and base alloy during drilling process. It is due to solid lubricant property of graphite which reduces the lesser thrust force, burr height and lower surface roughness. When machining with Carbide tool at low feed and high speeds good surface finish was obtained compared to other two types of cutting tool materials.

  18. In situ synthesis and formation mechanism of ZrC and ZrB2 by combustion synthesis from the Co-Zr-B4C system

    Directory of Open Access Journals (Sweden)

    Mengxian Zhang

    2015-09-01

    Full Text Available ZrC-ZrB2-based composites were prepared by combustion synthesis (CS reaction from 10 wt.% to 50 wt.% Co-Zr-B4C powder mixtures. With increasing Co contents, the particle sizes of near-spherical ZrC and platelet-like ZrB2 decreased from 1 μm to 0.5 μm and from 5 μm to 2 μm, respectively. In addition, the formation mechanism of ZrC and ZrB2 was explored by the phase transition and microstructure evolution on the combustion wave quenched sample in combination with differential scanning calorimeter analysis. The results showed that the production of ZrC was ascribed to the solid-solid reaction between Zr and C and the precipitation from the Co-Zr-B-C melt, while ZrB2 was prepared from the saturated liquid. The low B concentration in the Co-Zr-B-C liquid and high cooling rate during the CS process led to the presence of Co2B and ZrCo3B2 in the composites. The addition of Co in the Co-Zr-B4C system not only prevented ZrC and ZrB2 particulates from growing, but also promoted the occurrence of ZrC-ZrB2-forming reaction.

  19. Sliding-wear resistance of pure near fully-dense B4C under lubrication with water, diesel fuel, and paraffin oil

    DEFF Research Database (Denmark)

    Ortiz, Angel L.; Leal, Victor Manuel Candelario; Borrero-López, Oscar

    2017-01-01

    The sliding-wear resistance of pure near fully-dense B4C is investigated, and the wear mode/mechanisms identified, under lubrication with water, diesel fuel, and paraffin oil. It is found that the wear is mild in the three cases, with specific wear rates (SWRs) of 10−16–10−17 m3/N m. Nonetheless......, the wear resistance of the B4C ceramic is one order of magnitude greater under oil lubrication (1016 N m/m3) than under water lubrication (1015 N m/m3), and twice as great for the specific case of paraffin oil than diesel fuel, attributable to the lubricant’s viscosity. It is also found that the wear mode...... is always abrasion, and that the wear mechanisms are plastic deformation and localized fracture with grain pullout. However, in agreement with the macro-wear data, the severity of the wear damage is lower under lubrication with paraffin oil, followed by diesel fuel, and lastly water. Finally...

  20. Principles of Structure and Phase Composition Formation in Composite Master Alloys of the Al-Ti-B/B4c Systems Used for Aluminum Alloy Modification

    Science.gov (United States)

    Zhukov, I. A.; Promakhov, V. V.; Matveev, A. E.; Platov, V. V.; Khrustalev, A. P.; Dubkova, Ya. A.; Vorozhtsov, S. A.; Potekaev, A. I.

    2018-03-01

    The principles of formation of structure and properties of materials produced by self-propagating hightemperature synthesis (SHS) from the Al-Ti-B/B4C powder systems are identified. It is shown that the SHSmaterials produced from the Al-Ti-B powder systems consist of a TiAl intermetallic matrix with inclusions of titanium diboride particles. It is found out that an introduction of 1 wt.% of TiB2 particles into the melt of the AD35 aluminum alloy allows reducing the grain size from 620 to 220 μm and gives rise to an increase in the ultimate tensile strength of as-cast specimens from 100 to 145 MPa and in the plasticity from 7 to 9%.

  1. Reactivity determination of the Al2O3-B4C burnable poison as a function of its concentration in the IPEN/MB-01 reactor

    International Nuclear Information System (INIS)

    Giada, Marino Reis

    2005-01-01

    Burnable poison rods made of Al 2 O 3 -B 4 C pellets with different concentrations of 10 B have been manufactured for a set of experiments in the IPEN/MB-01 zero-power reactor. The experiments evaluated the reactivity of the burnable poison rods as a function of the 10 B concentration, and the shadowing effect on the control rod reactivity worth as a function of the distance between the burnable position rods and the control rod. The results showed that the burnable poison rods have a non-linear behavior as function of the 10 B concentration, starting to reach an asymptotic value for concentrations higher than 7 g/cm 3 of 10 B. The shadowing effect on the control rods was substantial. When the burnable poison rods were beside the control rod, its reactivity worth decreased as much as 30 %, and when they were 10,5 cm distant, the control rod worth decreased by 7 %. The MCNP results for the burnable poison reactivity effects agreed within experimental errors with the measured values. (author)

  2. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  3. Oxidative desulfurization: Kinetic modelling

    International Nuclear Information System (INIS)

    Dhir, S.; Uppaluri, R.; Purkait, M.K.

    2009-01-01

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H 2 O 2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel

  4. Creep behavior in interlaminar shear of a Hi-Nicalon™/SiC–B4C composite at 1200 °C in air and in steam

    International Nuclear Information System (INIS)

    Ruggles-Wrenn, M.B.; Pope, M.T.; Zens, T.W.

    2014-01-01

    Creep behavior in interlaminar shear of a non-oxide ceramic composite with a multilayered matrix was investigated at 1200 °C in laboratory air and in steam environment. The composite was produced via chemical vapor infiltration (CVI). The composite had an oxidation inhibited matrix, which consisted of alternating layers of silicon carbide and boron carbide and was reinforced with laminated Hi-Nicalon™ fibers woven in a five-harness-satin weave. Fiber preforms had pyrolytic carbon fiber coating with boron carbon overlay applied. The interlaminar shear properties were measured. The creep behavior was examined for interlaminar shear stresses in the 16–22 MPa range. Primary and secondary creep regimes were observed in all tests conducted in air and in steam. In air and in steam, creep run-out defined as 100 h at creep stress was achieved at 16 MPa. Similar creep strains were accumulated in air and in steam. Furthermore, creep strain rates and creep lifetimes were only moderately affected by the presence of steam. The retained properties of all specimens that achieved run-out were characterized. Composite microstructure, as well as damage and failure mechanisms were investigated. The tested specimens were also examined using electron probe microanalysis (EPMA) with wavelength dispersive spectroscopy (WDS). Analysis of the fracture surfaces revealed significant surface oxidation, but only trace amounts of boron and carbon. Cross sectional analysis showed increasing boron concentration in the specimen interior

  5. Susceptibility of Meningococcal Strains Responsible for Two Serogroup B Outbreaks on U.S. University Campuses to Serum Bactericidal Activity Elicited by the MenB-4C Vaccine.

    Science.gov (United States)

    Rossi, Raffaella; Beernink, Peter T; Giuntini, Serena; Granoff, Dan M

    2015-12-01

    In 2013 and 2014, two U.S. universities had meningococcal serogroup B outbreaks (a total of 14 cases) caused by strains from two different clonal complexes. To control the outbreaks, students were immunized with a serogroup B meningococcal vaccine (Novartis) that was not yet licensed in the United States. The vaccine (referred to as MenB-4C) contains four components capable of eliciting bactericidal activity. Both outbreak strains had high expression levels of two of the vaccine antigens (subfamily B factor H binding protein [FHbp] and neisserial heparin binding antigen [NHba]); the university B outbreak strain also had moderate expression of a third antigen, NadA. We investigated the bactericidal activity of sera from mice immunized with FHbp, NHba, or NadA and sera from MenB-4C-immunized infant macaques and an adult human. The postimmunization bactericidal activity of the macaque or human serum against isolates from university B with FHbp identification (ID) 1 that exactly matched the vaccine FHbp sequence variant was 8- to 21-fold higher than that against isolates from university A with FHbp ID 276 (96% identity to the vaccine antigen). Based on the bactericidal activity of mouse antisera to FHbp, NadA, or NHba and macaque or human postimmunization serum that had been depleted of anti-FHbp antibody, the bactericidal activity against both outbreak strains largely or entirely resulted from antibodies to FHbp. Thus, despite the high level of strain expression of FHbp from a subfamily that matched the vaccine antigen, there can be large differences in anti-FHbp bactericidal activity induced by MenB-4C vaccination. Further, strains with moderate to high NadA and/or NHba expression can be resistant to anti-NadA or anti-NHba bactericidal activity elicited by MenB-4C vaccination. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  6. In situ synthesis of TiB2-TiC particulates locally reinforced medium carbon steel-matrix composites via the SHS reaction of Ni-Ti-B4C system during casting

    International Nuclear Information System (INIS)

    Wang, H.Y.; Huang, L.; Jiang, Q.C.

    2005-01-01

    The fabrication of medium carbon steel-matrix composites locally reinforced with in situ TiB 2 -TiC particulates using self-propagating high-temperature synthesis (SHS) reaction of Ni-Ti-B 4 C system during casting was investigated. X-ray diffraction (XRD) results reveal that the exotherm of 1042 deg. C initiated by heat release of the solid state reaction in the differential thermal analysis (DTA) curve is an incomplete reaction in Ni-Ti-B 4 C system. As-cast microstructures of the in situ processed composites reveal a relatively uniform distribution of TiB 2 -TiC particulates in the locally reinforced regions. Furthermore, the particulate size and micro-porosity in the locally reinforced regions are significantly decreased with the increasing of the Ni content in the preforms. For a Ni content of 30 and 40 wt.%, near fully dense composites locally reinforced with in situ TiB 2 and TiC particulates can be fabricated. Although most of fine TiB 2 and TiC particulates which form by the reaction-precipitation mechanism during SHS reaction are present in the locally reinforced region, some large particulates which form by the nucleation-growth mechanism during solidification are entrapped inside the Fe-rich region located in the reinforcing region or inside the matrix region nearby the interface between matrix and reinforcing region. The hardness of the reinforcing region in the composite is significantly higher than that of the unreinforced medium carbon steel. Furthermore, the hardness values of the composites synthesized from 30 to 40 wt.% Ni-Ti-B 4 C systems are higher than those of the composites synthesized from 10 to 20 wt.% Ni-Ti-B 4 C systems

  7. Notch Sensitivity of Fatigue Behavior of a Hi-Nicalon™/SiC-B4C Composite at 1,200 °C in Air and in Steam

    Science.gov (United States)

    Ruggles-Wrenn, M. B.; Kurtz, G.

    2013-10-01

    The effect of holes on the fatigue life of a non-oxide ceramic composite processed via chemical vapor infiltration (CVI) was examined at 1,200 °C in laboratory air and in steam. The effect of holes on tensile strength at 1,200 °C was also evaluated. The composite comprised laminated woven Hi-Nicalon™ fibers in an oxidation inhibited matrix, which consisted of alternating layers of silicon carbide and boron carbide. Fiber preforms had pyrolytic carbon fiber coating with boron carbon overlay applied. Unnotched specimens and specimens with a center hole having a radius to width ratio of 0.24 were tested in tension-tension fatigue at 0.1 Hz and at 1.0 Hz. The fatigue stresses ranged from 100 to 140 MPa in air and in steam. Fatigue run-out was defined as 105 cycles at 0.1 Hz and as 2 × 105 cycles at 1.0 Hz. The net-section strength was less than the unnotched ultimate tensile strength. Comparison of notched and unnotched data also revealed that the fatigue performance was notch insensitive in both air and steam environments. Composite microstructure, as well as damage and failure mechanisms were investigated.

  8. The human polynucleotide kinase/phosphatase (hPNKP) inhibitor A12B4C3 radiosensitizes human myeloid leukemia cells to Auger electron-emitting anti-CD123 111In-NLS-7G3 radioimmunoconjugates

    International Nuclear Information System (INIS)

    Zereshkian, Arman; Leyton, Jeffrey V.; Cai, Zhongli; Bergstrom, Dane; Weinfeld, Michael; Reilly, Raymond M.

    2014-01-01

    Introduction: Leukemia stem cells (LSCs) are believed to be responsible for initiating and propagating acute myeloid leukemia (AML) and for causing relapse after treatment. Radioimmunotherapy (RIT) targeting these cells may improve the treatment of AML, but is limited by the low density of target epitopes. Our objective was to study a human polynucleotide kinase/phosphatase (hPNKP) inhibitor that interferes with DNA repair as a radiosensitizer for the Auger electron RIT agent, 111 In-NLS-7G3, which recognizes the CD123 + /CD131 - phenotype uniquely displayed by LSCs. Methods: The surviving fraction (SF) of CD123 + /CD131 - AML-5 cells exposed to 111 In-NLS-7G3 (33–266 nmols/L; 0.74 MBq/μg) or to γ-radiation (0.25-5 Gy) was determined by clonogenic assays. The effect of A12B4C3 (25 μmols/L) combined with 111 In-NLS-7G3 (16–66 nmols/L) or with γ-radiation (0.25–2 Gy) on the SF of AML-5 cells was assessed. The density of DNA double-strand breaks (DSBs) in the nucleus was measured using the γ-H2AX assay. Cellular dosimetry was estimated based on the subcellular distribution of 111 In-NLS-7G3 measured by cell fractionation. Results: Binding of 111 In-NLS-7G3 to AML-5 cells was reduced by 2.2-fold in the presence of an excess (1 μM) of unlabeled NLS-7G3, demonstrating specific binding to the CD123 + /CD131 - epitope. 111 In-NLS-7G3 reduced the SF of AML-5 cells from 86.1 ± 11.0% at 33 nmols/L to 10.5 ± 3.6% at 266 nmols/L. Unlabeled NLS-7G3 had no significant effect on the SF. Treatment of AML-5 cells with γ-radiation reduced the SF from 98.9 ± 14.9% at 0.25 Gy to 0.03 ± 0.1% at 5 Gy. A12B4C3 combined with 111 In-NLS-7G3 (16–66 nmols/L) enhanced the cytotoxicity up to 1.7-fold compared to treatment with radioimmunoconjugates alone and was associated with a 1.6-fold increase in DNA DSBs in the nucleus. A12B4C3 enhanced the cytotoxicity of γ-radiation (0.25–0.5 Gy) on AML-5 cells by up to 1.5-fold, and DNA DSBs were increased by 1.7-fold. Exposure to

  9. Model of dopant action in oxide cathodes

    International Nuclear Information System (INIS)

    Engelsen, Daniel den; Gaertner, Georg

    2005-01-01

    The paper describes an electrochemical model, which largely explains the formation of Ba in the oxide cathode at activation and normal operation. In a non-doped oxide cathode electrolysis of BaO is, besides the exchange reaction from the activators in the cathode nickel, an important source of Ba. By doping with rare earth oxides the conductivity of the oxide layer increases, which implies that the potential difference during current drawing over the oxide layer becomes lower and electrolysis of BaO is suppressed. This implies that the part of the electronic conductivity of the (Ba,Sr)O layer induced by the dopants also controls the sensitivity for poisoning: the higher the dopant level, the larger the sensitivity for poisoning. Furthermore, the suppression of electrolysis during normal operation largely explains why doped oxide cathodes have a better life performance than non-doped cathodes. Finally a hypothesis on the enhancement of sintering upon doping is presented

  10. Oxide behaviour modelling progress in COMETHE

    International Nuclear Information System (INIS)

    Vliet, J. van; Hoppe, N.

    1983-01-01

    An attempt has been made to develop a global model which simultaneously describes many important aspects of uranium oxide under irradiation. The individual models describing fuel structural changes, swelling and gas release, which were earlier separate from one another, are now part of a more realistic integral fuel model. Fission gas release depends now on an explicitely calculated open porosity, which is generated by fuel swelling; the latter is in turn connected to fission gas release. The paper describes the individual oxide models and how they are linked together. (author)

  11. Modelling of UO2 oxidation in steam

    International Nuclear Information System (INIS)

    Brito, A.C.; Iglesias, F.C.; Liu, Y.

    1996-01-01

    A computer model has been developed for calculating oxidation of UO 2 at high temperatures in steam oxidising conditions. Several methods to calculate the partial pressure of oxygen in the fuel and in the environment surrounding the fuel are available. The various methodologies have been compared and the best models have been compiled into a computer model which will be implemented into fuel thermal/mechanical behaviour codes such as FACTAR 2.0 (LOECI) and ELESIM/ELOCA. Calculations from the computer model have been compared to experimental results. The calculated oxidation reaction kinetics are in good agreement with the experimental data. (author)

  12. Selective Oxidation of Lignin Model Compounds.

    Science.gov (United States)

    Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

    2018-05-02

    Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Advanced oxidation processes: overall models

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, M. [Univ. de los Andes, Escuela Basica de Ingenieria, La Hechicera, Merida (Venezuela); Curco, D.; Addardak, A.; Gimenez, J.; Esplugas, S. [Dept. de Ingenieria Quimica. Univ. de Barcelona, Barcelona (Spain)

    2003-07-01

    Modelling AOPs implies to consider all the steps included in the process, that means, mass transfer, kinetic (reaction) and luminic steps. In this way, recent works develop models which relate the global reaction rate to catalyst concentration and radiation absorption. However, the application of such models requires to know what is the controlling step for the overall process. In this paper, a simple method is explained which allows to determine the controlling step. Thus, it is assumed that reactor is divided in two hypothetical zones (dark and illuminated), and according to the experimental results, obtained by varying only the reaction volume, it can be decided if reaction occurs only in the illuminated zone or in the all reactor, including dark zone. The photocatalytic degradation of phenol, by using titania degussa P-25 as catalyst, is studied as reaction model. The preliminary results obtained are presented here, showing that it seems that, in this case, reaction only occurs in the illuminated zone of photoreactor. A model is developed to explain this behaviour. (orig.)

  14. Investigation of Zircaloy-2 oxidation model for SFP accident analysis

    Energy Technology Data Exchange (ETDEWEB)

    Nemoto, Yoshiyuki, E-mail: nemoto.yoshiyuki@jaea.go.jp [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Kaji, Yoshiyuki; Ogawa, Chihiro; Kondo, Keietsu [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Nakashima, Kazuo; Kanazawa, Toru; Tojo, Masayuki [Global Nuclear Fuel – Japan Co., Ltd., 2-3-1, Uchikawa, Yokosuka-shi, Kanagawa, 239-0836 (Japan)

    2017-05-15

    The authors previously conducted thermogravimetric analyses on Zircaloy-2 in air. By using the thermogravimetric data, an oxidation model was constructed in this study so that it can be applied for the modeling of cladding degradation in spent fuel pool (SFP) severe accident condition. For its validation, oxidation tests of long cladding tube were conducted, and computational fluid dynamics analyses using the constructed oxidation model were proceeded to simulate the experiments. In the oxidation tests, high temperature thermal gradient along the cladding axis was applied and air flow rates in testing chamber were controlled to simulate hypothetical SFP accidents. The analytical outputs successfully reproduced the growth of oxide film and porous oxide layer on the claddings in oxidation tests, and validity of the oxidation model was proved. Influence of air flow rate for the oxidation behavior was thought negligible in the conditions investigated in this study. - Highlights: •An oxidation model of Zircaloy-2 in air environment was developed. •The oxidation model was validated by the comparison with oxidation tests using long cladding tubes in hypothetical spent fuel pool accident condition. •The oxidation model successfully reproduced the typical oxidation behavior in air.

  15. A temperature dependent ENDF/B-VI.8 ACE library for UO2, ThO2, Zirc4, SS AISI-348, H2O, B4C and Ag-In-Cd alloy

    International Nuclear Information System (INIS)

    Dalle, Hugo M.; Bianchini, Mario; Gomes, Paulo Cezar

    2009-01-01

    Most MCNP standard neutron ACE libraries are processed at room temperature, 293,6 deg K. The temperature enters into the processing of the evaluation of a data file through the Doppler broadening of cross-sections. The nuclear fuel burnup usually takes place at reactor core temperatures much higher than room temperature, consequently, Monte Carlo burnup calculations should not only use the best cross-sections evaluations available but also use evaluations that are at temperatures approximating the temperatures of the application. In order to face the scarcity of temperature dependent MCNP cross-sections data to most isotopes, CDTN is developing an in-house temperature dependent neutron library for those nuclides commonly necessary in the systems simulated for the ongoing projects demanding Monte Carlo burnup. This paper describes the data processing of the ENDF/B-VI, release 8, using the NJOY99 code, towards provides this temperature dependent ACE library. Up to now fifty one elements and isotopes of the materials uranium oxide, thorium oxide, zircaloy-4, stainless steel AISI-348, light water, boron carbide and the silver-indium-cadmium alloy were processed at temperatures range from 293,6 deg K to 1200 deg K. Some benchmarks for thorium cycle described in the 'OECD/NEA International Handbook of Evaluated Criticality Safety Benchmark Experiments' were simulated using MCNP5 and the data set of this in-house library and the results usually agree with those obtained for the .60c standard MCNP neutron library for room temperature. (author)

  16. Modelling the Krebs cycle and oxidative phosphorylation.

    Science.gov (United States)

    Korla, Kalyani; Mitra, Chanchal K

    2014-01-01

    The Krebs cycle and oxidative phosphorylation are the two most important sets of reactions in a eukaryotic cell that meet the major part of the total energy demands of a cell. In this paper, we present a computer simulation of the coupled reactions using open source tools for simulation. We also show that it is possible to model the Krebs cycle with a simple black box with a few inputs and outputs. However, the kinetics of the internal processes has been modelled using numerical tools. We also show that the Krebs cycle and oxidative phosphorylation together can be combined in a similar fashion - a black box with a few inputs and outputs. The Octave script is flexible and customisable for any chosen set-up for this model. In several cases, we had no explicit idea of the underlying reaction mechanism and the rate determining steps involved, and we have used the stoichiometric equations that can be easily changed as and when more detailed information is obtained. The script includes the feedback regulation of the various enzymes of the Krebs cycle. For the electron transport chain, the pH gradient across the membrane is an essential regulator of the kinetics and this has been modelled empirically but fully consistent with experimental results. The initial conditions can be very easily changed and the simulation is potentially very useful in a number of cases of clinical importance.

  17. Paraquat: model for oxidant-initiated toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Bus, J.S.; Gibson, J.E.

    1984-04-01

    Paraquat, a quaternary ammonium bipyridyl herbicide, produces degenerative lesions in the lung after systemic administration to man and animals. The pulmonary toxicity of paraquat resembles in several ways the toxicity of several other lung toxins, including oxygen, nitrofurantoin and bleomycin. Although a definitive mechanism of toxicity of parquat has not been delineated, a cyclic single electron reduction/oxidation of the parent molecule is a critical mechanistic event. The redox cycling of paraquat has two potentially important consequences relevant to the development of toxicity: generation of activated oxygen (e.g., superoxide anion, hydrogen perioxide, hydroxyl radical) which is highly reactive to cellular macromolecules; and/or oxidation of reducing equivalents (e.g., NADPH, reduced glutathione) necessary for normal cell function. Paraquat-induced pulmonary toxicity, therefore, is a potentially useful model for evaluation of oxidant mechanisms of toxicity. Furthermore, characterization of the consequences of intracellular redox cycling of xenobiotics will no doubt provide basic information regarding the role of this phenomena in the development of chemical toxicity. 105 references, 2 figures.

  18. Mathematical modeling of solid oxide fuel cells

    Science.gov (United States)

    Lu, Cheng-Yi; Maloney, Thomas M.

    1988-01-01

    Development of predictive techniques, with regard to cell behavior, under various operating conditions is needed to improve cell performance, increase energy density, reduce manufacturing cost, and to broaden utilization of various fuels. Such technology would be especially beneficial for the solid oxide fuel cells (SOFC) at it early demonstration stage. The development of computer models to calculate the temperature, CD, reactant distributions in the tubular and monolithic SOFCs. Results indicate that problems of nonuniform heat generation and fuel gas depletion in the tubular cell module, and of size limitions in the monolithic (MOD 0) design may be encountered during FC operation.

  19. MARMOT update for oxide fuel modeling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yongfeng [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schwen, Daniel [Idaho National Lab. (INL), Idaho Falls, ID (United States); Chakraborty, Pritam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Chao [Idaho National Lab. (INL), Idaho Falls, ID (United States); Aagesen, Larry [Idaho National Lab. (INL), Idaho Falls, ID (United States); Ahmed, Karim [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Wen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Biner, Bulent [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bai, Xianming [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Tonks, Michael [Pennsylvania State Univ., University Park, PA (United States); Millett, Paul [Univ. of Arkansas, Fayetteville, AR (United States)

    2016-09-01

    This report summarizes the lower-length-scale research and development progresses in FY16 at Idaho National Laboratory in developing mechanistic materials models for oxide fuels, in parallel to the development of the MARMOT code which will be summarized in a separate report. This effort is a critical component of the microstructure based fuel performance modeling approach, supported by the Fuels Product Line in the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program. The progresses can be classified into three categories: 1) development of materials models to be used in engineering scale fuel performance modeling regarding the effect of lattice defects on thermal conductivity, 2) development of modeling capabilities for mesoscale fuel behaviors including stage-3 gas release, grain growth, high burn-up structure, fracture and creep, and 3) improved understanding in material science by calculating the anisotropic grain boundary energies in UO$_2$ and obtaining thermodynamic data for solid fission products. Many of these topics are still under active development. They are updated in the report with proper amount of details. For some topics, separate reports are generated in parallel and so stated in the text. The accomplishments have led to better understanding of fuel behaviors and enhance capability of the MOOSE-BISON-MARMOT toolkit.

  20. Empirical soot formation and oxidation model

    Directory of Open Access Journals (Sweden)

    Boussouara Karima

    2009-01-01

    Full Text Available Modelling internal combustion engines can be made following different approaches, depending on the type of problem to be simulated. A diesel combustion model has been developed and implemented in a full cycle simulation of a combustion, model accounts for transient fuel spray evolution, fuel-air mixing, ignition, combustion, and soot pollutant formation. The models of turbulent combustion of diffusion flame, apply to diffusion flames, which one meets in industry, typically in the diesel engines particulate emission represents one of the most deleterious pollutants generated during diesel combustion. Stringent standards on particulate emission along with specific emphasis on size of emitted particulates have resulted in increased interest in fundamental understanding of the mechanisms of soot particulate formation and oxidation in internal combustion engines. A phenomenological numerical model which can predict the particle size distribution of the soot emitted will be very useful in explaining the above observed results and will also be of use to develop better particulate control techniques. A diesel engine chosen for simulation is a version of the Caterpillar 3406. We are interested in employing a standard finite-volume computational fluid dynamics code, KIVA3V-RELEASE2.

  1. Modeling Degradation in Solid Oxide Electrolysis Cells

    Energy Technology Data Exchange (ETDEWEB)

    Manohar S. Sohal; Anil V. Virkar; Sergey N. Rashkeev; Michael V. Glazoff

    2010-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic no equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, , within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, no equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  2. Model alloy oxidation in oxyfuel characteristic environment

    International Nuclear Information System (INIS)

    Coelho, D.; Rizzo, F.; Kranzmann, A.; Monteiro, M.; Caminha, I.

    2014-01-01

    In the oxyfuel process, pure oxygen is burned in boilers with recycled gas producing a gas rich in CO_2, making it easer to capture the CO_2 in the end of the process. The present work investigates the high temperature corrosion characteristics of a model Fe-Cr-Co alloy in typical oxyfuel process environment. Samples were oxidized at 600°C during 1000 hours in single atmosphere condition, where the samples is exposed to the same gas in all faces, and in a dual atmosphere condition, where the sample is exposed to water vapor in one side and to oxyfuel gas in the other. Samples where characterized by SEM and EDX. Results showed that corrosion is higher in a dual atmosphere condition than in single condition. (author)

  3. Atomization of JP-10/B4C gelled slurry fuel

    OpenAIRE

    Guglielmi, John David

    1992-01-01

    The atomization of a gelled boron slurry fuel using two commercially available airblast atomizers was studied at atmospheric pressure in non-reacting flow. The atomization of water was also characterized for comparison. Each atomizer was operated at two different liquid mass flow rates and several air/ fuel ratios. Drop size distribution was measured using a Malvern 2600 HSD Laser Diffraction Particle Sizer, Drop sizes acceptable for use in ramjet combustors could be obtained f...

  4. Multiscale model of metal alloy oxidation at grain boundaries

    International Nuclear Information System (INIS)

    Sushko, Maria L.; Alexandrov, Vitaly; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

    2015-01-01

    High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr 2 O 3 . This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl 2 O 4 . Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr 2 O 3 has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl 2 O 4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional

  5. Profiling the biological activity of oxide nanomaterials with mechanistic models

    NARCIS (Netherlands)

    Burello, E.

    2013-01-01

    In this study we present three mechanistic models for profiling the potential biological and toxicological effects of oxide nanomaterials. The models attempt to describe the reactivity, protein adsorption and membrane adhesion processes of a large range of oxide materials and are based on properties

  6. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  7. Modeling Manganese Sorption and Surface Oxidation During Filtration

    OpenAIRE

    Bierlein, Kevin Andrew

    2012-01-01

    Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the â natural greensand effect,â in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Mer...

  8. A Simplified Model for Volatile-N Oxidation

    DEFF Research Database (Denmark)

    Hansen, Stine; Glarborg, Peter

    2010-01-01

    In solid fuel flames, NO is largely formed from the oxidation of volatile nitrogen compounds such as HCN and NH3. To be able to model the nitrogen chemistry in these flames, it is necessary to have an adequate model for volatile-N oxidation. Simple global models for oxidation of HCN and NH3 from...... the literature should be used cautiously, since their predictive capabilities are limited, particularly under reducing conditions. Models for HCN/NH3/NO conversion based on the systematic reduction of a detailed chemical kinetic model offer high accuracy but rely on input estimates of combustion intermediates...... for the sub-bituminous and bituminous coals, especially at lower temperatures. The semiempirical correlations for estimating radical concentrations may also be useful in combination with models for other trace species, such as sulfur oxides, organic species, etc....

  9. A physiologically based kinetic model for bacterial sulfide oxidation.

    Science.gov (United States)

    Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

    2013-02-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Model for low temperature oxidation during long term interim storage

    Energy Technology Data Exchange (ETDEWEB)

    Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne [Service de la Corrosion et du Comportement des Materiaux dans leur Environnement, CEA/Saclay - 91191 Gif-sur-Yvette Cedex (France); Poquillon, Dominique; Monceau, Daniel [CIRIMAT UMR 5085, ENSIACET-INPT, 31077 Toulouse Cedex 4 (France)

    2004-07-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode during about one century. The metal lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies performed in the frame of the COCON program. An advanced model based on the description of elementary mechanisms involved in scale growth at low temperatures, like partial interfacial control of the oxidation kinetics and/or grain boundary diffusion, is developed in order to increase the reliability of the long term extrapolations deduced from basic models developed from short time experiments. Since only few experimental data on dry oxidation are available in the temperature range of interest, experiments have also been performed to evaluate the relevant input parameters for models like grain size of oxide scale, considering iron as simplified material. (authors)

  11. Model for low temperature oxidation during long term interim storage

    International Nuclear Information System (INIS)

    Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne; Poquillon, Dominique; Monceau, Daniel

    2004-01-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode during about one century. The metal lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies performed in the frame of the COCON program. An advanced model based on the description of elementary mechanisms involved in scale growth at low temperatures, like partial interfacial control of the oxidation kinetics and/or grain boundary diffusion, is developed in order to increase the reliability of the long term extrapolations deduced from basic models developed from short time experiments. Since only few experimental data on dry oxidation are available in the temperature range of interest, experiments have also been performed to evaluate the relevant input parameters for models like grain size of oxide scale, considering iron as simplified material. (authors)

  12. Advanced methods of solid oxide fuel cell modeling

    CERN Document Server

    Milewski, Jaroslaw; Santarelli, Massimo; Leone, Pierluigi

    2011-01-01

    Fuel cells are widely regarded as the future of the power and transportation industries. Intensive research in this area now requires new methods of fuel cell operation modeling and cell design. Typical mathematical models are based on the physical process description of fuel cells and require a detailed knowledge of the microscopic properties that govern both chemical and electrochemical reactions. ""Advanced Methods of Solid Oxide Fuel Cell Modeling"" proposes the alternative methodology of generalized artificial neural networks (ANN) solid oxide fuel cell (SOFC) modeling. ""Advanced Methods

  13. A mechanistic model on methane oxidation in the rice rhizosphere

    NARCIS (Netherlands)

    Bodegom, van P.M.; Leffelaar, P.A.; Goudriaan, J.

    2001-01-01

    A mechanistic model is presented on the processes leading to methane oxidation in rice rhizosphere. The model is driven by oxygen release from a rice root into anaerobic rice soil. Oxygen is consumed by heterotrophic and methanotrophic respiration, described by double Monod kinetics, and by iron

  14. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...

  15. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  16. Modeling of thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode

    Science.gov (United States)

    Heydari, F.; Maghsoudipour, A.; Alizadeh, M.; Khakpour, Z.; Javaheri, M.

    2015-09-01

    Artificial intelligence models have the capacity to eliminate the need for expensive experimental investigation in various areas of manufacturing processes, including the material science. This study investigates the applicability of adaptive neuro-fuzzy inference system (ANFIS) approach for modeling the performance parameters of thermal expansion coefficient (TEC) of perovskite oxide for solid oxide fuel cell cathode. Oxides (Ln = La, Nd, Sm and M = Fe, Ni, Mn) have been prepared and characterized to study the influence of the different cations on TEC. Experimental results have shown TEC decreases favorably with substitution of Nd3+ and Mn3+ ions in the lattice. Structural parameters of compounds have been determined by X-ray diffraction, and field emission scanning electron microscopy has been used for the morphological study. Comparison results indicated that the ANFIS technique could be employed successfully in modeling thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode, and considerable savings in terms of cost and time could be obtained by using ANFIS technique.

  17. Modeling of nitrous oxide production by autotrophic ammonia-oxidizing bacteria with multiple production pathways.

    Science.gov (United States)

    Ni, Bing-Jie; Peng, Lai; Law, Yingyu; Guo, Jianhua; Yuan, Zhiguo

    2014-04-01

    Autotrophic ammonia oxidizing bacteria (AOB) have been recognized as a major contributor to N2O production in wastewater treatment systems. However, so far N2O models have been proposed based on a single N2O production pathway by AOB, and there is still a lack of effective approach for the integration of these models. In this work, an integrated mathematical model that considers multiple production pathways is developed to describe N2O production by AOB. The pathways considered include the nitrifier denitrification pathway (N2O as the final product of AOB denitrification with NO2(-) as the terminal electron acceptor) and the hydroxylamine (NH2OH) pathway (N2O as a byproduct of incomplete oxidation of NH2OH to NO2(-)). In this model, the oxidation and reduction processes are modeled separately, with intracellular electron carriers introduced to link the two types of processes. The model is calibrated and validated using experimental data obtained with two independent nitrifying cultures. The model satisfactorily describes the N2O data from both systems. The model also predicts shifts of the dominating pathway at various dissolved oxygen (DO) and nitrite levels, consistent with previous hypotheses. This unified model is expected to enhance our ability to predict N2O production by AOB in wastewater treatment systems under varying operational conditions.

  18. Effects of Oxidation on Oxidation-Resistant Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-05-01

    The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

  19. Developments in kinetic modelling of chalcocite particle oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jaervi, J; Ahokainen, T; Jokilaakso, A [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

    1998-12-31

    A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

  20. Developments in kinetic modelling of chalcocite particle oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

    1997-12-31

    A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

  1. Alternative model for the Great Oxidation Event

    Science.gov (United States)

    Bekker, A.

    2014-12-01

    Transition from the Archean, largely anoxic atmosphere and ocean to the Proterozoic oxidizing surface conditions has been inferred in Zimbabwe from the geochemical and geological evidence as early as 1927. Subsequent studies provided additional support for this interpretation, bracketed the transition between 2.45 and 2.32 Ga, and suggested temporal and cause-and-effect relationship with a series of the early Paleoproterozoic ice ages (including 4 discrete events). Recently recognized transient oxidation events of the Archean add texture to this pattern, but do not change it. The rise of atmospheric oxygen requires a misbalance between oxygen sinks and sources and most attention was focused on sinks. In contrast, change in oxygen supply related to low organic productivity in Archean oceans with limited nutrient contents are considered here. Although carbon isotope values of carbonates and organic carbon indicate substantial relative burial rate of organic carbon during the Archean, most of the earlier buried organic matter at that time was recycled to sediments during continental weathering, implying very low productivity and burial of 'new' organic carbon. Low contents of redox-sensitive elements, such as Mo, Cu, Zn, and V, in Archean seawater could have kept organic productivity and oxygen production at low levels. The GOE was immediately preceded by deposition of giant iron formations, accounting for more than 70% of world iron resources, and worldwide emplacement of a number of LIPs between 2.5 and 2.45 Ga, indicating enhanced delivery of nutrients and redox-sensitive elements to the oceans via submarine hydrothermal processes and continental weathering under CO2- and SO2-rich atmosphere and associated terrestrial acidic runoff. This enhanced emplacement of LIPs has been linked with the growth of continental crust, emergence of the first supercontinent, and mantle overturn at the Archean-Proterozoic boundary. The GOE could have thus been triggered by enhanced

  2. Can polymer thermal oxidative ageing be modelled?

    International Nuclear Information System (INIS)

    Audouin, L.; Colin, X.; Fayolle, B.; Richaud, E.; Verdu, J.

    2010-01-01

    It has been supposed, for a long time, that kinetic modelling of polymer ageing for nonempirical lifetime prediction was out of reach for two main reasons: hyper-complexity of mechanisms and heterogeneity of reactions. The arguments relative to both aspects are examined here. It is concluded that, thanks to recent advances, especially the introduction of numerical methods, kinetic modelling is possible in various important practical cases. (authors)

  3. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  4. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

    Hoorn, J.A.A.; van Soolingen, J.; Versteeg, G. F.

    The kinetics of the oxidation of toluene have been studied in close interaction with the gas-liquid mass transfer occurring in the reactor. Kinetic parameters for a simple model have been estimated on basis of experimental observations performed under industrial conditions. The conclusions for the

  5. Modelling the change in the oxidation coefficient during the aerobic ...

    African Journals Online (AJOL)

    In this work the aerobic degradation of phenol by acclimated activated sludge was studied. Results demonstrate that while the phenol removal rate by acclimated activated sludge follows the Monod model, the oxygen uptake rate obeys a Haldane-type equation. The phenol oxidation coefficient obtained at different intial ...

  6. A conceptual model for the fuel oxidation of defective fuel

    International Nuclear Information System (INIS)

    Higgs, J.D.; Lewis, B.J.; Thompson, W.T.; He, Z.

    2007-01-01

    A mechanistic conceptual model has been developed to predict the fuel oxidation behaviour in operating defective fuel elements for water-cooled nuclear reactors. This theoretical work accounts for gas-phase transport and sheath reactions in the fuel-to-sheath gap to determine the local oxygen potential. An improved thermodynamic analysis has also been incorporated into the model to describe the equilibrium state of the oxidized fuel. The fuel oxidation kinetics treatment accounts for multi-phase transport including normal diffusion and thermodiffusion for interstitial oxygen migration in the solid, as well as gas-phase transport in the fuel pellet cracks. The fuel oxidation treatment is further coupled to a heat conduction equation. A numerical solution of the coupled transport equations is obtained by a finite-element technique with the FEMLAB 3.1 software package. The model is able to provide radial-axial profiles of the oxygen-to-uranium ratio and the fuel temperatures as a function of time in the defective element for a wide range of element powers and defect sizes. The model results are assessed against coulometric titration measurements of the oxygen-to-metal profile for pellet samples taken from ten spent defective elements discharged from the National Research Universal Reactor at the Chalk River Laboratories and commercial reactors

  7. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  8. Oxidative stress of crystalline lens in rat menopausal model

    OpenAIRE

    Acer, Semra; Pekel, Gökhan; Küçükatay, Vural; Karabulut, Aysun; Yağcı, Ramazan; Çetin, Ebru Nevin; Akyer, Şahika Pınar; Şahin, Barbaros

    2016-01-01

    ABSTRACT Purpose: To evaluate lenticular oxidative stress in rat menopausal models. Methods: Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1). From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2), 10 were administered a daily injection of methylprednisolone until the end of the study (Gro...

  9. A model of pyritic oxidation in waste rock dumps

    International Nuclear Information System (INIS)

    Davis, G.B.; Ritchie, A.I.M.

    1983-01-01

    The oxidation of pyrite can lead to high acid levels and high concentrations of trace metals in the water that runs off and percolates through pyritic material. This is the situation at the abandoned uranium mine at Rum Jungle in the Northern Territory of Australia, where pyritic oxidation in the waste rock dumps resulting from open cut mining of the uranium orebody has led to pollution of the nearby East Branch of the Finniss River, with trace metals such as copper, manganese and zinc. Mathematical equations are formulated which describe a model of pyritic oxidation within a waste rock dump, where it is assumed that oxygen transport is the rate limiting step in the oxidation process and that oxygen is transported by gaseous diffusion through the pore space of the dump, followed by diffusion into oxidation sites within the particles that comprise the dump. The equations have been solved numerically assuming values for such parameters as porosity, sulphur density and oxygen diffusion coefficients which are applicable to the waste rock dumps at Rum Jungle. An approximate solution to the equations is also presented. Calculations of the heat source distribution and the total SO 4 production rate are presented for both single size particles and for a range of particle sizes in the dump. The usefulness of the approximate solution, and of calculations based on single size particles in the dump in assessing the effectiveness of strategies to reduce pollution from such waste rock dumps are discussed

  10. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-12-01

    Full Text Available Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by

  11. A microkinetic model of the methanol oxidation over silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2003-01-01

    A simple microkinetic model for the oxidation of methanol on silver based on surface science studies at UHV and low temperatures has been formulated. The reaction mechanism is a simple Langmuir-Hinshelwood mechanism, with one type of active oxygen and one route to formaldehyde and carbon dioxide......, respectively. The model explains observed reaction orders, selectivity, apparent activation enthalpies and the choice of industrial reaction conditions. More interesting the model disproves the notion that the mechanism deduced from surface science in UHV cannot be responsible for formaldehyde synthesis...

  12. Impedance Modeling of Solid Oxide Fuel Cell Cathodes

    DEFF Research Database (Denmark)

    Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

    2010-01-01

    A 1-dimensional impedance model for a solid oxide fuel cell cathode is formulated and applied to a cathode consisting of 50/50 wt% strontium doped lanthanum cobaltite and gadolinia doped ceria. A total of 42 impedance spectra were recorded in the temperature range: 555-852°C and in the oxygen...... partial pressure range 0.028-1.00 atm. The recorded impedance spectra were successfully analyzed using the developed impedance model in the investigated temperature and oxygen partial pressure range. It is also demonstrated that the model can be used to predict how impedance spectra evolve with different...

  13. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  14. Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys

    Energy Technology Data Exchange (ETDEWEB)

    London, A.J., E-mail: andrew.london@materials.ox.ac.uk [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Lozano-Perez, S.; Moody, M.P. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Amirthapandian, S.; Panigrahi, B.K.; Sundar, C.S. [Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, TN (India); Grovenor, C.R.M. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom)

    2015-12-15

    Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471–503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174–1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe–0.3Y{sub 2}O{sub 3}, Fe–0.2Ti–0.3Y{sub 2}O{sub 3} and Fe–14Cr–0.2Ti–0.3Y{sub 2}O{sub 3}. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors.

  15. Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys.

    Science.gov (United States)

    London, A J; Lozano-Perez, S; Moody, M P; Amirthapandian, S; Panigrahi, B K; Sundar, C S; Grovenor, C R M

    2015-12-01

    Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471-503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174-1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe-0.3Y2O3, Fe-0.2Ti-0.3Y2O3 and Fe-14Cr-0.2Ti-0.3Y2O3. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Oxidation protection and behavior of in-situ zirconium diboride–silicon carbide coating for carbon/carbon composites

    International Nuclear Information System (INIS)

    Li, Lu; Li, Hejun; Yin, Xuemin; Chu, Yanhui; Chen, Xi; Fu, Qiangang

    2015-01-01

    Highlights: • ZrB 2 –SiC coating was prepared on C/C composite by in-situ reaction. • A two-layered structure was obtained when the coating was oxidized at 1500 °C. • The formation and collapse of bubbles influenced the coating oxidation greatly. • The morphology evolution of oxide scale during oxidation was illuminated. - Abstract: To protect carbon/carbon (C/C) composites against oxidation, zirconium diboride–silicon carbide (ZrB 2 –SiC) coating was prepared by in-situ reaction using ZrC, B 4 C and Si as raw materials. The in-situ ZrB 2 –SiC coated C/C presented good oxidation resistance, whose weight loss was only 0.15% after isothermal oxidation at 1500 °C for 216 h. Microstructure evolution of coating at 1500 °C was studied, revealing a two-layered structure: (1) ZrO 2 (ZrSiO 4 ) embedded in SiO 2 -rich glass, and (2) unaffected ZrB 2 –SiC. The formation and collapse of bubbles influenced the coating oxidation greatly. A model based on the evolution of oxide scale was proposed to explain the failure mechanism of coating

  17. Evaluating four mathematical models for nitrous oxide production by autotrophic ammonia-oxidizing bacteria.

    Science.gov (United States)

    Ni, Bing-Jie; Yuan, Zhiguo; Chandran, Kartik; Vanrolleghem, Peter A; Murthy, Sudhir

    2013-01-01

    There is increasing evidence showing that ammonia-oxidizing bacteria (AOB) are major contributors to N(2)O emissions from wastewater treatment plants (WWTPs). Although the fundamental metabolic pathways for N(2)O production by AOB are now coming to light, the mechanisms responsible for N(2)O production by AOB in WWTP are not fully understood. Mathematical modeling provides a means for testing hypotheses related to mechanisms and triggers for N(2)O emissions in WWTP, and can then also become a tool to support the development of mitigation strategies. This study examined the ability of four mathematical model structures to describe two distinct mechanisms of N(2)O production by AOB. The production mechanisms evaluated are (1) N(2)O as the final product of nitrifier denitrification with NO(2)- as the terminal electron acceptor and (2) N(2)O as a byproduct of incomplete oxidation of hydroxylamine (NH(2)OH) to NO(2)-. The four models were compared based on their ability to predict N(2)O dynamics observed in three mixed culture studies. Short-term batch experimental data were employed to examine model assumptions related to the effects of (1) NH4+ concentration variations, (2) dissolved oxygen (DO) variations, (3) NO(2)- accumulations and (4) NH(2OH as an externally provided substrate. The modeling results demonstrate that all these models can generally describe the NH4+, NO(2)-, and NO(3)- data. However, none of these models were able to reproduce all measured N(2)O data. The results suggest that both the denitrification and NH(2)OH pathways may be involved in N(2)O production and could be kinetically linked by a competition for intracellular reducing equivalents. A unified model capturing both mechanisms and their potential interactions needs to be developed with consideration of physiological complexity. Copyright © 2012 Wiley Periodicals, Inc.

  18. Transgenic Mouse Model for Reducing Oxidative Damage in Bone

    Science.gov (United States)

    Schreurs, Ann-Sofie; Torres, S.; Truong, T.; Moyer, E. L.; Kumar, A.; Tahimic, Candice C. G.; Alwood, J. S.; Limoli, C. L.; Globus, R. K.

    2016-01-01

    Bone loss can occur due to many challenges such age, radiation, microgravity, and Reactive Oxygen Species (ROS) play a critical role in bone resorption by osteoclasts (Bartell et al. 2014). We hypothesize that suppression of excess ROS in skeletal cells, both osteoblasts and osteoclasts, regulates skeletal growth and remodeling. To test our hypothesis, we used transgenic mCAT mice which overexpress the human anti-oxidant catalase gene targeted to the mitochondria, the main site for endogenous ROS production. mCAT mice have a longer life-span than wildtype controls and have been used to study various age-related disorders. To stimulate remodeling, 16 week old mCAT mice or wildtype mice were exposed to treatment (hindlimb-unloading and total body-irradiation) or sham treatment conditions (control). Tissues were harvested 2 weeks later for skeletal analysis (microcomputed tomography), biochemical analysis (gene expression and oxidative damage measurements), and ex vivo bone marrow derived cell culture (osteoblastogenesis and osteoclastogenesis). mCAT mice expressed the transgene and displayed elevated catalase activity in skeletal tissue and marrow-derived osteoblasts and osteoclasts grown ex vivo. In addition, when challenged with treatment, bone tissues from wildtype mice showed elevated levels of malondialdehyde (MDA), indicating oxidative damage) whereas mCAT mice did not. Correlation analysis revealed that increased catalase activity significantly correlated with decreased MDA levels and that increased oxidative damage correlated with decreased percent bone volume (BVTV). In addition, ex-vivo cultured osteoblast colony growth correlated with catalase activity in the osteoblasts. Thus, we showed that these transgenic mice can be used as a model to study the relationship between markers of oxidative damage and skeletal properties. mCAT mice displayed reduced BVTV and trabecular number relative to wildtype mice, as well as increased structural model index in the

  19. Advanced impedance modeling of solid oxide electrochemical cells

    DEFF Research Database (Denmark)

    Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Impedance spectroscopy is a powerful technique for detailed study of the electrochemical and transport processes that take place in fuel cells and electrolysis cells, including solid oxide cells (SOCs). Meaningful analysis of impedance measurements is nontrivial, however, because a large number...... techniques to provide good guesses for the modeling parameters, like transforming the impedance data to the distribution of relaxation times (DRT), together with experimental parameter sensitivity studies, is the state-of-the-art approach to achieve good EC model fits. Here we present new impedance modeling...... electrode and 2-D gas transport models which have fewer unknown parameters for the same number of processes, (ii) use of a new model fitting algorithm, “multi-fitting”, in which multiple impedance spectra are fit simultaneously with parameters linked based on the variation of measurement conditions, (iii...

  20. The Lightning Nitrogen Oxides Model (LNOM): Status and Recent Applications

    Science.gov (United States)

    Koshak, William; Khan, Maudood; Peterson, Harold

    2011-01-01

    Improvements to the NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) are discussed. Recent results from an August 2006 run of the Community Multiscale Air Quality (CMAQ) modeling system that employs LNOM lightning NOx (= NO + NO2) estimates are provided. The LNOM analyzes Lightning Mapping Array (LMA) data to estimate the raw (i.e., unmixed and otherwise environmentally unmodified) vertical profile of lightning NOx. The latest LNOM estimates of (a) lightning channel length distributions, (b) lightning 1-m segment altitude distributions, and (c) the vertical profile of NOx are presented. The impact of including LNOM-estimates of lightning NOx on CMAQ output is discussed.

  1. Asymptotically exact solution of a local copper-oxide model

    International Nuclear Information System (INIS)

    Zhang Guangming; Yu Lu.

    1994-03-01

    We present an asymptotically exact solution of a local copper-oxide model abstracted from the multi-band models. The phase diagram is obtained through the renormalization-group analysis of the partition function. In the strong coupling regime, we find an exactly solved line, which crosses the quantum critical point of the mixed valence regime separating two different Fermi-liquid (FL) phases. At this critical point, a many-particle resonance is formed near the chemical potential, and a marginal-FL spectrum can be derived for the spin and charge susceptibilities. (author). 15 refs, 1 fig

  2. Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships

    NARCIS (Netherlands)

    Wachs, I.E.; Jehng, J.M.; Deo, G.; Weckhuysen, B.M.; Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

    1997-01-01

    The oxidation of n-butane to maleic anhydride was investigated over a series of model-supported vanadia catalysts where the vanadia phase was present as a two-dimensional metal oxide overlayer on the different oxide supports (TiO2, ZrO2, CeO2, Nb2O5, Al2O3, and SiO2). No correlation was found

  3. Oxidative stress of crystalline lens in rat menopausal model.

    Science.gov (United States)

    Acer, Semra; Pekel, Gökhan; Küçükatay, Vural; Karabulut, Aysun; Yağcı, Ramazan; Çetin, Ebru Nevin; Akyer, Şahika Pınar; Şahin, Barbaros

    2016-01-01

    To evaluate lenticular oxidative stress in rat menopausal models. Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1). From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2), 10 were administered a daily injection of methylprednisolone until the end of the study (Group 3), and the remaining 10 rats were administered intraperitoneal streptozocin to induce diabetes mellitus (Group 4). Total oxidant status (TOS), total antioxidant capacity (TAC), and oxidative stress index (OSI) measurements of the crystalline lenses were analyzed. The mean OSI was the lowest in group 1 and highest in group 4. Nevertheless, the difference between the groups was not statistically significant in terms of OSI (p >0.05). The mean TOS values were similar between the groups (p >0.05), whereas the mean TAC of group 1 was significantly higher than that of the other groups (p <0.001). Our results indicate that menopause may not promote cataract formation.

  4. Oxidative stress of crystalline lens in rat menopausal model

    Directory of Open Access Journals (Sweden)

    Semra Acer

    Full Text Available ABSTRACT Purpose: To evaluate lenticular oxidative stress in rat menopausal models. Methods: Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1. From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2, 10 were administered a daily injection of methylprednisolone until the end of the study (Group 3, and the remaining 10 rats were administered intraperitoneal streptozocin to induce diabetes mellitus (Group 4. Total oxidant status (TOS, total antioxidant capacity (TAC, and oxidative stress index (OSI measurements of the crystalline lenses were analyzed. Results: The mean OSI was the lowest in group 1 and highest in group 4. Nevertheless, the difference between the groups was not statistically significant in terms of OSI (p >0.05. The mean TOS values were similar between the groups (p >0.05, whereas the mean TAC of group 1 was significantly higher than that of the other groups (p <0.001. Conclusions: Our results indicate that menopause may not promote cataract formation.

  5. Discrete Event System Based Pyroprocessing Modeling and Simulation: Oxide Reduction

    International Nuclear Information System (INIS)

    Lee, H. J.; Ko, W. I.; Choi, S. Y.; Kim, S. K.; Hur, J. M.; Choi, E. Y.; Im, H. S.; Park, K. I.; Kim, I. T.

    2014-01-01

    Dynamic changes according to the batch operation cannot be predicted in an equilibrium material flow. This study began to build a dynamic material balance model based on the previously developed pyroprocessing flowsheet. As a mid- and long-term research, an integrated pyroprocessing simulator is being developed at the Korea Atomic Energy Research Institute (KAERI) to cope with a review on the technical feasibility, safeguards assessment, conceptual design of facility, and economic feasibility evaluation. The most fundamental thing in such a simulator development is to establish the dynamic material flow framework. This study focused on the operation modeling of pyroprocessing to implement a dynamic material flow. As a case study, oxide reduction was investigated in terms of a dynamic material flow. DES based modeling was applied to build a pyroprocessing operation model. A dynamic material flow as the basic framework for an integrated pyroprocessing was successfully implemented through ExtendSim's internal database and item blocks. Complex operation logic behavior was verified, for example, an oxide reduction process in terms of dynamic material flow. Compared to the equilibrium material flow, a model-based dynamic material flow provides such detailed information that a careful analysis of every batch is necessary to confirm the dynamic material balance results. With the default scenario of oxide reduction, the batch mass balance was verified in comparison with a one-year equilibrium mass balance. This study is still under progress with a mid-and long-term goal, the development of a multi-purpose pyroprocessing simulator that is able to cope with safeguards assessment, economic feasibility, technical evaluation, conceptual design, and support of licensing for a future pyroprocessing facility

  6. A Structural Molar Volume Model for Oxide Melts Part III: Fe Oxide-Containing Melts

    Science.gov (United States)

    Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

    2016-04-01

    As part III of this series, the model is extended to iron oxide-containing melts. All available experimental data in the FeO-Fe2O3-Na2O-K2O-MgO-CaO-MnO-Al2O3-SiO2 system were critically evaluated based on the experimental condition. The variations of FeO and Fe2O3 in the melts were taken into account by using FactSage to calculate the Fe2+/Fe3+ distribution. The molar volume model with unary and binary model parameters can be used to predict the molar volume of the molten oxide of the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-FeO-Fe2O3-Al2O3-SiO2 system in the entire range of compositions, temperatures, and oxygen partial pressures from Fe saturation to 1 atm pressure.

  7. LG Solid Oxide Fuel Cell (SOFC) Model Development

    Energy Technology Data Exchange (ETDEWEB)

    Haberman, Ben [LG Fuel Cell Systems Inc., North Canton, OH (United States); Martinez-Baca, Carlos [LG Fuel Cell Systems Inc., North Canton, OH (United States); Rush, Greg [LG Fuel Cell Systems Inc., North Canton, OH (United States)

    2013-05-31

    This report presents a summary of the work performed by LG Fuel Cell Systems Inc. during the project LG Solid Oxide Fuel Cell (SOFC) Model Development (DOE Award Number: DE-FE0000773) which commenced on October 1, 2009 and was completed on March 31, 2013. The aim of this project is for LG Fuel Cell Systems Inc. (formerly known as Rolls-Royce Fuel Cell Systems (US) Inc.) (LGFCS) to develop a multi-physics solid oxide fuel cell (SOFC) computer code (MPC) for performance calculations of the LGFCS fuel cell structure to support fuel cell product design and development. A summary of the initial stages of the project is provided which describes the MPC requirements that were developed and the selection of a candidate code, STAR-CCM+ (CD-adapco). This is followed by a detailed description of the subsequent work program including code enhancement and model verification and validation activities. Details of the code enhancements that were implemented to facilitate MPC SOFC simulations are provided along with a description of the models that were built using the MPC and validated against experimental data. The modeling work described in this report represents a level of calculation detail that has not been previously available within LGFCS.

  8. Magnetism-tuning strategies for graphene oxide based on magnetic oligoacene oxide patches model.

    Science.gov (United States)

    Wen, Yanjie; Yen, Chia-Liang; Yan, Linyin; Kono, Hirohiko; Lin, Sheng-Hsien; Ling, Yong-Chien

    2018-01-31

    Graphene oxide (GO) has wide application potential owing to its 2D structure and diverse modification sites for various targeted uses. The introduction of magnetism into GO structures has further advanced the controllability of the application of GO materials. Herein, the concept of modular design and modeling was applied to tune the magnetism of GO. To obtain desirable magnetic properties, diradical-structured GO patches were formed by the introduction of two functional groups to break the Kekule structure of the benzene ring. In these diradical GO patches, the energy of the triplet state was lower than those of the open-shell broken-symmetry singlet state and closed-shell singlet state. To create such multi-radical patches, a practical approach is to determine a substantial spatial separation of the α and β spin densities in the molecule. Thus, systematic design strategies and tests were evaluated. The first strategy was extending the distance between the distribution center of the α and β spin densities; the second was controlling the delocalization directions of the α and β electrons; the third was controlling the delocalization extension of the α and β electrons by oxidative modification, and finally introducing multi-radical structures into the molecular system and controlling the position of each radical. Herein, successful molecular models with a large magnetic coupling constant (∼3600 cm -1 ) were obtained. This study paves the way to explore ferromagnetic MGO guided by theoretical study, which may become reality soon.

  9. The chemical energy unit partial oxidation reactor operation simulation modeling

    Science.gov (United States)

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

    2018-01-01

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

  10. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  11. Application of the GRI 1.2 Methane Oxidation Model to Methane and Methanol Oxidation in Supercritical Water

    National Research Council Canada - National Science Library

    Rice, Steven

    1997-01-01

    The Gas Research Institute (GRI) has been leading an effort over the past few years to consolidate recent developments in the elementary reaction modeling of the oxidation of methane for combustion applications into a single...

  12. NMR relaxation induced by iron oxide particles: testing theoretical models.

    Science.gov (United States)

    Gossuin, Y; Orlando, T; Basini, M; Henrard, D; Lascialfari, A; Mattea, C; Stapf, S; Vuong, Q L

    2016-04-15

    Superparamagnetic iron oxide particles find their main application as contrast agents for cellular and molecular magnetic resonance imaging. The contrast they bring is due to the shortening of the transverse relaxation time T 2 of water protons. In order to understand their influence on proton relaxation, different theoretical relaxation models have been developed, each of them presenting a certain validity domain, which depends on the particle characteristics and proton dynamics. The validation of these models is crucial since they allow for predicting the ideal particle characteristics for obtaining the best contrast but also because the fitting of T 1 experimental data by the theory constitutes an interesting tool for the characterization of the nanoparticles. In this work, T 2 of suspensions of iron oxide particles in different solvents and at different temperatures, corresponding to different proton diffusion properties, were measured and were compared to the three main theoretical models (the motional averaging regime, the static dephasing regime, and the partial refocusing model) with good qualitative agreement. However, a real quantitative agreement was not observed, probably because of the complexity of these nanoparticulate systems. The Roch theory, developed in the motional averaging regime (MAR), was also successfully used to fit T 1 nuclear magnetic relaxation dispersion (NMRD) profiles, even outside the MAR validity range, and provided a good estimate of the particle size. On the other hand, the simultaneous fitting of T 1 and T 2 NMRD profiles by the theory was impossible, and this occurrence constitutes a clear limitation of the Roch model. Finally, the theory was shown to satisfactorily fit the deuterium T 1 NMRD profile of superparamagnetic particle suspensions in heavy water.

  13. Dynamic global model of oxide Czochralski process with weighing control

    Science.gov (United States)

    Mamedov, V. M.; Vasiliev, M. G.; Yuferev, V. S.

    2011-03-01

    A dynamic model of oxide Czochralski growth with weighing control has been developed for the first time. A time-dependent approach is used for the calculation of temperature fields in different parts of a crystallization set-up and convection patterns in a melt, while internal radiation in crystal is considered in a quasi-steady approximation. A special algorithm is developed for the calculation of displacement of a triple point and simulation of a crystal surface formation. To calculate variations in the heat generation, a model of weighing control with a commonly used PID regulator is applied. As an example, simulation of the growth process of gallium-gadolinium garnet (GGG) crystals starting from the stage of seeding is performed.

  14. Thermal radiation modelling in a tubular solid oxide fuel cell

    International Nuclear Information System (INIS)

    Austin, M.E.; Pharoah, J.G.; Vandersteen, J.D.J.

    2004-01-01

    Solid Oxide Fuel Cells (SOFCs) are becoming the fuel cell of choice among companies and research groups interested in small power generation units. Questions still exist, however, about the operating characteristics of these devices; in particular the temperature distribution in the fuel cell. Using computational fluid dynamics (CFD) a model is proposed that incorporates conduction, convection and radiation. Both surface-to-surface and participating media are considered. It is hoped that a more accurate account of the temperature field in the various flow channels and cell components will be made to assist work on design of fuel cell components and reaction mechanisms. The model, when incorporating radiative heat transfer with participating media, predicts substantially lower operating temperatures and smaller temperature gradients than it does without these equations. It also shows the importance of the cathode air channel in cell cooling. (author)

  15. An experimental and modeling study of diethyl carbonate oxidation

    KAUST Repository

    Nakamura, Hisashi; Curran, Henry J.; Polo-Có rdoba, Á ngel David; Pitz, William J.; Dagaut, P.; Togbé , Casimir; Sarathy, Mani; Mehl, Marco; Agudelo, John Ramiro; Bustamante, Felipe

    2015-01-01

    Diethyl carbonate (DEC) is an attractive biofuel that can be used to displace petroleum-derived diesel fuel, thereby reducing CO2 and particulate emissions from diesel engines. A better understanding of DEC combustion characteristics is needed to facilitate its use in internal combustion engines. Toward this goal, ignition delay times for DEC were measured at conditions relevant to internal combustion engines using a rapid compression machine (RCM) and a shock tube. The experimental conditions investigated covered a wide range of temperatures (660-1300K), a pressure of 30bar, and equivalence ratios of 0.5, 1.0 and 2.0 in air. To provide further understanding of the intermediates formed in DEC oxidation, species concentrations were measured in a jet-stirred reactor at 10atm over a temperature range of 500-1200K and at equivalence ratios of 0.5, 1.0 and 2.0. These experimental measurements were used to aid the development and validation of a chemical kinetic model for DEC.The experimental results for ignition in the RCM showed near negative temperature coefficient (NTC) behavior. Six-membered alkylperoxy radical (RO˙2) isomerizations are conventionally thought to initiate low-temperature branching reactions responsible for NTC behavior, but DEC has no such possible 6- and 7-membered ring isomerizations. However, its molecular structure allows for 5-, 8- and 9-membered ring RO˙2 isomerizations. To provide accurate rate constants for these ring structures, ab initio computations for RO˙2⇌Q˙OOH isomerization reactions were performed. These new RO˙2 isomerization rate constants have been implemented in a chemical kinetic model for DEC oxidation. The model simulations have been compared with ignition delay times measured in the RCM near the NTC region. Results of the simulation were also compared with experimental results for ignition in the high-temperature region and for species concentrations in the jet-stirred reactor. Chemical kinetic insights into the

  16. An experimental and modeling study of diethyl carbonate oxidation

    KAUST Repository

    Nakamura, Hisashi

    2015-04-01

    Diethyl carbonate (DEC) is an attractive biofuel that can be used to displace petroleum-derived diesel fuel, thereby reducing CO2 and particulate emissions from diesel engines. A better understanding of DEC combustion characteristics is needed to facilitate its use in internal combustion engines. Toward this goal, ignition delay times for DEC were measured at conditions relevant to internal combustion engines using a rapid compression machine (RCM) and a shock tube. The experimental conditions investigated covered a wide range of temperatures (660-1300K), a pressure of 30bar, and equivalence ratios of 0.5, 1.0 and 2.0 in air. To provide further understanding of the intermediates formed in DEC oxidation, species concentrations were measured in a jet-stirred reactor at 10atm over a temperature range of 500-1200K and at equivalence ratios of 0.5, 1.0 and 2.0. These experimental measurements were used to aid the development and validation of a chemical kinetic model for DEC.The experimental results for ignition in the RCM showed near negative temperature coefficient (NTC) behavior. Six-membered alkylperoxy radical (RO˙2) isomerizations are conventionally thought to initiate low-temperature branching reactions responsible for NTC behavior, but DEC has no such possible 6- and 7-membered ring isomerizations. However, its molecular structure allows for 5-, 8- and 9-membered ring RO˙2 isomerizations. To provide accurate rate constants for these ring structures, ab initio computations for RO˙2⇌Q˙OOH isomerization reactions were performed. These new RO˙2 isomerization rate constants have been implemented in a chemical kinetic model for DEC oxidation. The model simulations have been compared with ignition delay times measured in the RCM near the NTC region. Results of the simulation were also compared with experimental results for ignition in the high-temperature region and for species concentrations in the jet-stirred reactor. Chemical kinetic insights into the

  17. Modeling of oxide reduction in repeated-batch pyroprocessing

    International Nuclear Information System (INIS)

    Lee, Hyo Jik; Im, Hun Suk; Park, Geun Il

    2016-01-01

    Highlights: • Pyroprocessing is a complicated batch-type operation. • Discrete event system modeling was used to create an integrated operation model. • Simulation showed that could be accomplished. • The dynamic material flow helps us understand the process operation. • We showed that complex material flow could be simulated in terms of mass balance. - Abstract: Pyroprocessing is a complicated batch-type operation, involving a highly complex material flow logic with a huge number of unit processes. Discrete event system modeling was used to create an integrated operation model for which simulation showed that dynamic material flow could be accomplished to provide considerable insight into the process operation. In the model simulation, the amount of material transported upstream and downstream in the process satisfies a mass balance equation while considering the hold-up incurred by every batch operation. This study also simulated, in detail, an oxide reduction group process embracing electrolytic reduction, cathode processing, and salt purification. Based on the default operation scenario, it showed that complex material flows could be precisely simulated in terms of the mass balance. Specifically, the amount of high-heat elements remaining in the molten salt bath is analyzed to evaluate the operation scenario.

  18. Modeling of termokinetic oscillations at partial oxidation of methane

    Science.gov (United States)

    Arutyunov, A. V.; Belyaev, A. A.; Inovenkov, I. N.; Nefedov, V. V.

    2017-12-01

    Partial oxidation of natural gas at moderate temperatures below 1500 K has significant interest for a number of industrial applications. But such processes can proceed at different unstable regimes including oscillating modes. Nonlinear phenomena at partial oxidation of methane were observed at different conditions. The investigation of the complex nonlinear system of equations that describes this process is a real method to insure its stability at industrial conditions and, at the same time, is an effective tool for its further enhancement. Numerical analysis of methane oxidation kinetics in the continuous stirred-tank reactor, with the use of detailed kinetic model has shown the possibility of the appearance of oscillating modes in the appropriate range of reaction parameters that characterize the composition, pressure, reagents flow, thermophysical features of the system, and geometry of the reactor. The appearance of oscillating modes is connected both with the reaction kinetics, heat release and sink and reagents introduction and removing. At that, oscillations appear only at a limited range of parameters, but can be accompanied by significant change in the yield of products. We have determined the range of initial temperature and pressure at which oscillations can be observed, if all other parameters remained fixed. The boundaries of existence of oscillations on the phase plane were calculated. It was shown that depending on the position inside the oscillation region the oscillations have different frequency and amplitude. It was reviled the role of heat exchange with the environment: at the absence of heat exchange the oscillating modes are impossible. In the vicinity of the boundary of phase range, where oscillations exist, significant change of concentration of some products were observed, for example, that of CO2, which in this case one of the principal products is. At that, insignificant increase in pressure not only change the character of CO2 behaving

  19. Modeling of Cd(II) sorption on mixed oxide

    International Nuclear Information System (INIS)

    Waseem, M.; Mustafa, S.; Naeem, A.; Shah, K.H.; Hussain, S.Y.; Safdar, M.

    2011-01-01

    Mixed oxide of iron and silicon (0.75 M Fe(OH)3:0.25 M SiO/sub 2/) was synthesized and characterized by various techniques like surface area analysis, point of zero charge (PZC), energy dispersive X-rays (EDX) spectroscopy, Thermogravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared spectroscopy (FTIR) and X-rays diffraction (XRD) analysis. The uptake of Cd/sup 2+/ ions on mixed oxide increased with pH, temperature and metal ion concentration. Sorption data have been interpreted in terms of both Langmuir and Freundlich models. The Xm values at pH 7 are found to be almost twice as compared to pH 5. The values of both DH and DS were found to be positive indicating that the sorption process was endothermic and accompanied by the dehydration of Cd/sup 2+/. Further, the negative value of DG confirms the spontaneity of the reaction. The ion exchange mechanism was suggested to take place for each Cd/sup 2+/ ions at pH 5, whereas ion exchange was found coupled with non specific adsorption of metal cations at pH 7. (author)

  20. The role of lager beer yeast in oxidative stability of model beer

    DEFF Research Database (Denmark)

    Berner, Torben Sune; Arneborg, Nils

    2012-01-01

    that the oxidative stress resistance was strain dependent. Fermentation of model wort in European Brewing Convention tubes using three yeast strains with varying oxidative stress resistances resulted in three model beers with different rates of radical formation as measured by electron spin resonance in forced......AIMS: In this study, we investigated the relationship between the ability of lager brewing yeast strains to tolerate oxidative stress and their ability to produce oxidative stable model beer. METHODS AND RESULTS: Screening of 21 lager brewing yeast strains against diamide and paraquat showed...... in the model beers. CONCLUSIONS: A more oxidative stable beer is not obtained by a more-oxidative-stress-tolerant lager brewing yeast strain, exhibiting a higher secretion of thioredoxin, but rather by a less-oxidative-stress-tolerant strain, exhibiting a higher iron uptake. SIGNIFICANCE AND IMPACT...

  1. Oxidation Resistant Graphite Studies

    Energy Technology Data Exchange (ETDEWEB)

    W. Windes; R. Smith

    2014-07-01

    The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

  2. Modeling Degradation in Solid Oxide Electrolysis Cells - Volume II

    Energy Technology Data Exchange (ETDEWEB)

    Manohar Motwani

    2011-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential,, within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, non-equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  3. Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

    Science.gov (United States)

    Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

    2018-08-01

    The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Reactor modeling and process analysis for partial oxidation of natural gas

    NARCIS (Netherlands)

    Albrecht, B.A.

    2004-01-01

    This thesis analyses a novel process of partial oxidation of natural gas and develops a numerical tool for the partial oxidation reactor modeling. The proposed process generates syngas in an integrated plant of a partial oxidation reactor, a syngas turbine and an air separation unit. This is called

  5. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  6. Systemic oxidative stress markers in animal model for depression

    DEFF Research Database (Denmark)

    Bouzinova, Elena; Kravtsova, Violetta; Aalkjær, Christian

    Involvement of oxidative stress (OxS) in development of major depressive disorder has recently become evident, though mechanisms behind this remain elusive. We analyzed therefore OxS pathways in rat Chronic Mild Stress (CMS) model of depression. Rats are exposed to chronic unpredictable mild...... mg/kg/day). Saline injections were done to control the vehicle effect. Escitalopram treated rats were sub-divided into 2 groups: responders and non-responders, according to their hedonic state and compared to non-stressed rats, treated with either saline or Escitalopram. Measurement of total...... glutathione and malondialdehyde (MDA) in lungs, heart, skeletal muscles, liver, saphenous, mesenteric, and tail arteries were used as estimates for OxS. In heart, glutathione was increased in CMS rats in comparison with non-stressed vehicle group. Accordingly, an estimate for free radical activity, MDA...

  7. Oxidation of boron carbide at high temperatures

    International Nuclear Information System (INIS)

    Steinbrueck, Martin

    2005-01-01

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

  8. SPH based modelling of oxide and oxide film formation in gravity die castings

    International Nuclear Information System (INIS)

    Ellingsen, K; M'Hamdi, M; Coudert, T

    2015-01-01

    Gravity die casting is an important casting process which has the capability of making complicated, high-integrity components for e.g. the automotive industry. Oxides and oxide films formed during filling affect the cast product quality. The Smoothed particle hydrodynamics (SPH) method is particularly suited to follow complex flows. The SPH method has been used to study filling of a gravity die including the formation and transport of oxides and oxide films for two different filling velocities. A low inlet velocity leads to a higher amount of oxides and oxide films in the casting. The study demonstrates the usefulness of the SPH method for an increased understanding of the effect of different filling procedures on the cast quality. (paper)

  9. Ultrasound assisted synthesis of nanocrystalline zinc oxide: Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Mongia [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Farhat, Samir, E-mail: farhat@lspm.cnrs.fr [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Schoenstein, Frederic; Karmous, Farah; Jouini, Noureddine [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Viana, Bruno [LCMCP Chimie-Paristech, UPMC, Collège de France, 11 Rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Mgaidi, Arbi [Laboratoire de chimie minérale industrielle université Tunis el Manar (Tunisia)

    2014-12-05

    Highlights: • ZnO nanospheres and nanowires were grown using ultrasound and thermal activation techniques. • The growth uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). • A thermochemical model was developed based on thermodynamic equilibrium calculations. • We estimate species distribution in the bubble in temperature range from 5000 K to ambient. • We propose a new mechanism for ZnO growth assisted by ultrasound irradiation. - Abstract: A fast and green approach is proposed for the preparation of nanocrystalline zinc oxide (ZnO) via ultrasonic (US) irradiation in polyol medium. The process uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). The protocol is compared to thermal activation under the same chemical environment. The activation method is found to be playing a critical role in the selective synthesis of morphologically distinct nanostructures. As compared to thermally activated conventional polyol process, (US) permits to considerably reduce reaction time as well as size of particles. In addition, the shape of these nanoparticles was changed from long nanowires to small nanospheres, indicating different reaction mechanisms. To explain this difference, a thermochemical model was developed based on thermodynamic equilibrium calculations. The model estimate species distribution in the bubble in temperature range from 5000 K to ambient simulating quenching process during bubble formation and collapse. Our results indicate the presence of high density of zinc atoms that could be responsible of a high density of nucleation as compared to thermal activation.

  10. Ultrasound assisted synthesis of nanocrystalline zinc oxide: Experiments and modelling

    International Nuclear Information System (INIS)

    Hosni, Mongia; Farhat, Samir; Schoenstein, Frederic; Karmous, Farah; Jouini, Noureddine; Viana, Bruno; Mgaidi, Arbi

    2014-01-01

    Highlights: • ZnO nanospheres and nanowires were grown using ultrasound and thermal activation techniques. • The growth uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). • A thermochemical model was developed based on thermodynamic equilibrium calculations. • We estimate species distribution in the bubble in temperature range from 5000 K to ambient. • We propose a new mechanism for ZnO growth assisted by ultrasound irradiation. - Abstract: A fast and green approach is proposed for the preparation of nanocrystalline zinc oxide (ZnO) via ultrasonic (US) irradiation in polyol medium. The process uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). The protocol is compared to thermal activation under the same chemical environment. The activation method is found to be playing a critical role in the selective synthesis of morphologically distinct nanostructures. As compared to thermally activated conventional polyol process, (US) permits to considerably reduce reaction time as well as size of particles. In addition, the shape of these nanoparticles was changed from long nanowires to small nanospheres, indicating different reaction mechanisms. To explain this difference, a thermochemical model was developed based on thermodynamic equilibrium calculations. The model estimate species distribution in the bubble in temperature range from 5000 K to ambient simulating quenching process during bubble formation and collapse. Our results indicate the presence of high density of zinc atoms that could be responsible of a high density of nucleation as compared to thermal activation

  11. A comprehensive experimental and modeling study of isobutene oxidation

    KAUST Repository

    Zhou, Chong-Wen

    2016-03-17

    Isobutene is an important intermediate in the pyrolysis and oxidation of higher-order branched alkanes, and it is also a component of commercial gasolines. To better understand its combustion characteristics, a series of ignition delay time (IDT) and laminar flame speed (LFS) measurements have been performed. In addition, flow reactor speciation data recorded for the pyrolysis and oxidation of isobutene is also reported. Predictions of an updated kinetic model described herein are compared with each of these data sets, as well as with existing jet-stirred reactor (JSR) species measurements. IDTs of isobutene oxidation were measured in four different shock tubes and in two rapid compression machines (RCMs) under conditions of relevance to practical combustors. The combination of shock tube and RCM data greatly expands the range of available validation data for isobutene oxidation models to pressures of 50 atm and temperatures in the range 666–1715 K. Isobutene flame speeds were measured experimentally at 1 atm and at unburned gas temperatures of 298–398 K over a wide range of equivalence ratios. For the flame speed results, there was good agreement between different facilities and the current model in the fuel-rich region. Ab initio chemical kinetics calculations were carried out to calculate rate constants for important reactions such as H-atom abstraction by hydroxyl and hydroperoxyl radicals and the decomposition of 2-methylallyl radicals. A comprehensive chemical kinetic mechanism has been developed to describe the combustion of isobutene and is validated by comparison to the presently considered experimental measurements. Important reactions, highlighted via flux and sensitivity analyses, include: (a) hydrogen atom abstraction from isobutene by hydroxyl and hydroperoxyl radicals, and molecular oxygen; (b) radical–radical recombination reactions, including 2-methylallyl radical self-recombination, the recombination of 2-methylallyl radicals with

  12. Phase-field modeling of corrosion kinetics under dual-oxidants

    Science.gov (United States)

    Wen, You-Hai; Chen, Long-Qing; Hawk, Jeffrey A.

    2012-04-01

    A phase-field model is proposed to simulate corrosion kinetics under a dual-oxidant atmosphere. It will be demonstrated that the model can be applied to simulate corrosion kinetics under oxidation, sulfidation and simultaneous oxidation/sulfidation processes. Phase-dependent diffusivities are incorporated in a natural manner and allow more realistic modeling as the diffusivities usually differ by many orders of magnitude in different phases. Simple free energy models are then used for testing the model while calibrated free energy models can be implemented for quantitative modeling.

  13. Mathematical modeling of oxygen transport in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Svensson, Ann Mari

    1997-12-31

    This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

  14. Modeling of the Nitric Oxide Transport in the Human Lungs.

    Science.gov (United States)

    Karamaoun, Cyril; Van Muylem, Alain; Haut, Benoît

    2016-01-01

    In the human lungs, nitric oxide (NO) acts as a bronchodilatator, by relaxing the bronchial smooth muscles and is closely linked to the inflammatory status of the lungs, owing to its antimicrobial activity. Furthermore, the molar fraction of NO in the exhaled air has been shown to be higher for asthmatic patients than for healthy patients. Multiple models have been developed in order to characterize the NO dynamics in the lungs, owing to their complex structure. Indeed, direct measurements in the lungs are difficult and, therefore, these models are valuable tools to interpret experimental data. In this work, a new model of the NO transport in the human lungs is proposed. It belongs to the family of the morphological models and is based on the morphometric model of Weibel (1963). When compared to models published previously, its main new features are the layered representation of the wall of the airways and the possibility to simulate the influence of bronchoconstriction (BC) and of the presence of mucus on the NO transport in lungs. The model is based on a geometrical description of the lungs, at rest and during a respiratory cycle, coupled with transport equations, written in the layers composing an airway wall and in the lumen of the airways. First, it is checked that the model is able to reproduce experimental information available in the literature. Second, the model is used to discuss some features of the NO transport in healthy and unhealthy lungs. The simulation results are analyzed, especially when BC has occurred in the lungs. For instance, it is shown that BC can have a significant influence on the NO transport in the tissues composing an airway wall. It is also shown that the relation between BC and the molar fraction of NO in the exhaled air is complex. Indeed, BC might lead to an increase or to a decrease of this molar fraction, depending on the extent of the BC and on the possible presence of mucus. This should be confirmed experimentally and might

  15. Glutamine prevents oxidative stress in a model of portal hypertension.

    Science.gov (United States)

    Zabot, Gilmara Pandolfo; Carvalhal, Gustavo Franco; Marroni, Norma Possa; Licks, Francielli; Hartmann, Renata Minuzzo; da Silva, Vinícius Duval; Fillmann, Henrique Sarubbi

    2017-07-07

    To evaluate the protective effects of glutamine in a model of portal hypertension (PH) induced by partial portal vein ligation (PPVL). Male Wistar rats were housed in a controlled environment and were allowed access to food and water ad libitum . Twenty-four male Wistar rats were divided into four experimental groups: (1) control group (SO) - rats underwent exploratory laparotomy; (2) control + glutamine group (SO + G) - rats were subjected to laparotomy and were treated intraperitoneally with glutamine; (3) portal hypertension group (PPVL) - rats were subjected to PPVL; and (4) PPVL + glutamine group (PPVL + G) - rats were treated intraperitoneally with glutamine for seven days. Local injuries were determined by evaluating intestinal segments for oxidative stress using lipid peroxidation and the activities of glutathione peroxidase (GPx), endothelial nitric oxide synthase (eNOS) and inducible nitric oxide synthase (iNOS) after PPVL. Lipid peroxidation of the membrane was increased in the animals subjected to PH ( P 0.05). The activity of the antioxidant enzyme GTx was decreased in the gut of animals subjected to PH compared with that in the control group of animals not subjected to PH ( P 0.05). At least 10 random, non-overlapping images of each histological slide with 200 × magnification (44 pixel = 1 μm) were captured. The sum means of all areas, of each group were calculated. The mean areas of eNOS staining for both of the control groups were similar. The PPVL group showed the largest area of staining for eNOS. The PPVL + G group had the second highest amount of staining, but the mean value was much lower than that of the PPVL group ( P < 0.01). For iNOS, the control (SO) and control + G (SO + G) groups showed similar areas of staining. The PPVL group contained the largest area of iNOS staining, followed by the PPVL + G group; however, this area was significantly smaller than that of the group that underwent PH without glutamine ( P < 0.01). Treatment with

  16. Transgenic Mouse Model for Reducing Oxidative Damage in Bone

    Science.gov (United States)

    Schreurs, A.-S.; Torres, S.; Truong, T.; Kumar, A.; Alwood, J. S.; Limoli, C. L.; Globus, R. K.

    2014-01-01

    Exposure to musculoskeletal disuse and radiation result in bone loss; we hypothesized that these catabolic treatments cause excess reactive oxygen species (ROS), and thereby alter the tight balance between bone resorption by osteoclasts and bone formation by osteoblasts, culminating in bone loss. To test this, we used transgenic mice which over-express the human gene for catalase, targeted to mitochondria (MCAT). Catalase is an anti-oxidant that converts the ROS hydrogen peroxide into water and oxygen. MCAT mice were shown previously to display reduced mitochondrial oxidative stress and radiosensitivity of the CNS compared to wild type controls (WT). As expected, MCAT mice expressed the transgene in skeletal tissue, and in marrow-derived osteoblasts and osteoclast precursors cultured ex vivo, and also showed greater catalase activity compared to wildtype (WT) mice (3-6 fold). Colony expansion in marrow cells cultured under osteoblastogenic conditions was 2-fold greater in the MCAT mice compared to WT mice, while the extent of mineralization was unaffected. MCAT mice had slightly longer tibiae than WT mice (2%, P less than 0.01), although cortical bone area was slightly lower in MCAT mice than WT mice (10%, p=0.09). To challenge the skeletal system, mice were treated by exposure to combined disuse (2 wk Hindlimb Unloading) and total body irradiation Cs(137) (2 Gy, 0.8 Gy/min), then bone parameters were analyzed by 2-factor ANOVA to detect possible interaction effects. Treatment caused a 2-fold increase (p=0.015) in malondialdehyde levels of bone tissue (ELISA) in WT mice, but had no effect in MCAT mice. These findings indicate that the transgene conferred protection from oxidative damage caused by treatment. Unexpected differences between WT and MCAT mice emerged in skeletal responses to treatment.. In WT mice, treatment did not alter osteoblastogenesis, cortical bone area, moment of inertia, or bone perimeter, whereas in MCAT mice, treatment increased these

  17. Finite element modelling of the oxidation kinetics of Zircaloy-4 with a controlled metal-oxide interface and the influence of growth stress

    International Nuclear Information System (INIS)

    Zumpicchiat, Guillaume; Pascal, Serge; Tupin, Marc; Berdin-Méric, Clotilde

    2015-01-01

    Highlights: We developed two finite element models of zirconium-based alloy oxidation using the CEA Cast3M code to simulate the oxidation kinetics of Zircaloy-4: the diffuse interface model and the sharp interface model. We also studied the effect of stresses on the oxidation kinetics. The main results are: • Both models lead to parabolic oxidation kinetics in agreement with the Wagner’s theory. • The modellings enable to calculate the stress distribution in the oxide as well as in the metal. • A strong effect of the hydrostatic stress on the oxidation kinetics has been evidenced. • The stress gradient effect changes the parabolic kinetics into a sub-parabolic law closer to the experimental kinetics because of the stress gradient itself, but also because of the growth stress increase with the oxide thickness. - Abstract: Experimentally, zirconium-based alloys oxidation kinetics is sub-parabolic, by contrast with the Wagner theory which predicts a parabolic kinetics. Two finite element models have been developed to simulate this phenomenon: the diffuse interface model and the sharp interface model. Both simulate parabolic oxidation kinetics. The growth stress effects on oxygen diffusion are studied to try to explain the gap between theory and experience. Taking into account the influence of the hydrostatic stress and its gradient into the oxygen flux expression, sub-parabolic oxidation kinetics have been simulated. The sub-parabolic behaviour of the oxidation kinetics can be explained by a non-uniform compressive stress level into the oxide layer.

  18. Modelling nitrous oxide emissions from grazed grassland systems

    International Nuclear Information System (INIS)

    Wang Junye; Cardenas, Laura M.; Misselbrook, Tom H.; Cuttle, Steve; Thorman, Rachel E.; Li Changsheng

    2012-01-01

    Grazed grassland systems are an important component of the global carbon cycle and also influence global climate change through their emissions of nitrous oxide and methane. However, there are huge uncertainties and challenges in the development and parameterisation of process-based models for grazed grassland systems because of the wide diversity of vegetation and impacts of grazing animals. A process-based biogeochemistry model, DeNitrification-DeComposition (DNDC), has been modified to describe N 2 O emissions for the UK from regional conditions. This paper reports a new development of UK-DNDC in which the animal grazing practices were modified to track their contributions to the soil nitrogen (N) biogeochemistry. The new version of UK-DNDC was tested against datasets of N 2 O fluxes measured at three contrasting field sites. The results showed that the responses of the model to changes in grazing parameters were generally in agreement with observations, showing that N 2 O emissions increased as the grazing intensity increased. - Highlights: ► Parameterisation of grazing system using grazing intensity. ► Modification of UK D NDC for the UK soil and weather conditions. ► Validation of the UK D NDC against measured data of N 2 O emissions in three UK sites. ► Estimating influence of animal grazing practises on N 2 O emissions. - Grazing system was parameterised using grazing intensity and UK-DNDC model was modified and validated against measured data of N 2 O emissions in three UK sites.

  19. Physical chemistry and modelling of the sintering of actinide oxides

    International Nuclear Information System (INIS)

    Lechelle, Jacques

    2013-01-01

    This report gives a synthesis of the work I have carried out or to which I have numerically contributed to from 1996 up to 2012 in the Department of Plutonium Uranium and minor Actinides in Cadarache CEA Center. Their main goal is the study and the modeling of the sintering process of nuclear fuels which is the unifying thread of this document. Both in order to take into account the physical and chemical features of the actinide bearing oxide material and in order to combine the different transport phenomena leading to sintering, a sub-granular scale model is under development. Extension to a varying chemical composition as well as exchanges with the gaseous phase are foreseen. A simulation on a larger scale (pellet scale) is ongoing in the framework of a PhD thesis. Validation means have been tested with (U,Pu)O 2 material on the scale of the pellet (Small Angle Neutron Diffusion), on the scale of powder granules (X-Ray High Resolution Micro-Tomography) and with CeO 2 at the 'Institut de Chimie Separative' in Marcoule on a single crystal scale (Environmental Scanning Electron Microscope). The required microstructure homogeneity for nuclear fuels has led to a campaign of experimental studies about the role of Cr 2 O 3 as a sintering aid. Whole of these studies improve our understanding of fuel sintering and hence leads to an improved mastering of this process. (author) [fr

  20. Chemical interactions at the interfaces of Mo/B4C/Si/B4C multilayers upon low-temperature annealing

    NARCIS (Netherlands)

    Nyabero, S.L.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

    2012-01-01

    Interactions at interfaces in thin films and multilayers play an important role for present day nano-scaled devices. For example, reducing thermally induced interdiffusion between Mo and Si layers is a key challenge in developing Mo/Si multilayers as reflective coatings for projection lithography

  1. Modeling of Alkane Oxidation Using Constituents and Species

    Science.gov (United States)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

    It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical

  2. Nonlinear Model Predictive Control for Solid Oxide Fuel Cell System Based On Wiener Model

    OpenAIRE

    T. H. Lee; J. H. Park; S. M. Lee; S. C. Lee

    2010-01-01

    In this paper, we consider Wiener nonlinear model for solid oxide fuel cell (SOFC). The Wiener model of the SOFC consists of a linear dynamic block and a static output non-linearity followed by the block, in which linear part is approximated by state-space model and the nonlinear part is identified by a polynomial form. To control the SOFC system, we have to consider various view points such as operating conditions, another constraint conditions, change of load current and so on. A change of ...

  3. Novel Magnetic Zinc Oxide Nanotubes for Phenol Adsorption: Mechanism Modeling

    Directory of Open Access Journals (Sweden)

    Marwa F. Elkady

    2017-11-01

    Full Text Available Considering the great impact of a material’s surface area on adsorption processes, hollow nanotube magnetic zinc oxide with a favorable surface area of 78.39 m2/g was fabricated with the assistance of microwave technology in the presence of poly vinyl alcohol (PVA as a stabilizing agent followed by sonic precipitation of magnetite nano-particles. Scanning electron microscopy (SEM and transmission electron microscopy (TEM micrographs identified the nanotubes’ morphology in the synthesized material with an average aspect ratio of 3. X-ray diffraction (XRD analysis verified the combination of magnetite material with the hexagonal wurtzite structure of ZnO in the prepared material. The immobilization of magnetite nanoparticles on to ZnO was confirmed using vibrating sample magnetometry (VSM. The sorption affinity of the synthesized magnetic ZnO nanotube for phenolic compounds from aqueous solutions was examined as a function of various processing factors. The degree of acidity of the phenolic solution has great influence on the phenol sorption process on to magnetic ZnO. The calculated value of ΔH0 designated the endothermic nature of the phenol uptake process on to the magnetic ZnO nanotubes. Mathematical modeling indicated a combination of physical and chemical adsorption mechanisms of phenolic compounds on to the fabricated magnetic ZnO nanotubes. The kinetic process correlated better with the second-order rate model compared to the first-order rate model. This result indicates the predominance of the chemical adsorption process of phenol on to magnetic ZnO nanotubes.

  4. A conceptual and calculational model for gas formation from impure calcined plutonium oxides

    International Nuclear Information System (INIS)

    Lyman, John L.; Eller, P. Gary

    2000-01-01

    Safe transport and storage of pure and impure plutonium oxides requires an understanding of processes that may generate or consume gases in a confined storage vessel. We have formulated conceptual and calculational models for gas formation from calcined materials. The conceptual model for impure calcined plutonium oxides is based on the data collected to date

  5. Photoelectrolysis at the oxide-electrolyte interface as interpreted through the 'transition' layer model

    Science.gov (United States)

    Kalia, R. K.; Weber, Michael F.; Schumacher, L.; Dignam, M. J.

    1980-12-01

    A transition layer model of the oxide-electrolyte interface, proposed earlier by one of us, is outlined and then examined in the light of experimental data relating primarily to photoelectrolysis of water at semiconducting oxide electrodes. The model provides useful insight into the behaviour of the system and allows a calculation of thc minimum bias potential needed for photoelectrolysis, thus illuminating the origin of the requirement for such an external bias. In order to electrolyse water without a bias, the model requires an n-type oxide to be sufficiently reduced so that it is thermodynamically capable of chemically reducing water to produce hydrogen at 1 atm pressure. Similarly, for bias-free operation, a p-type metal oxide must be thermodynamically unstable with respect to the release of oxygen at 1 atm pressure. In the face of these requirements it is apparent that oxide stability is bound to be in general a serious problem for nonstoichiometric single metal oxides.

  6. Modelling of low energy ion sputtering from oxide surfaces

    International Nuclear Information System (INIS)

    Kubart, T; Nyberg, T; Berg, S

    2010-01-01

    The main aim of this work is to present a way to estimate the values of surface binding energy for oxides. This is done by fitting results from the binary collisions approximation code Tridyn with data from the reactive sputtering processing curves, as well as the elemental composition obtained from x-ray photoelectron spectroscopy (XPS). Oxide targets of Al, Ti, V, Nb and Ta are studied. The obtained surface binding energies are then used to predict the partial sputtering yields. Anomalously high sputtering yield is observed for the TiO 2 target. This is attributed to the high sputtering yield of Ti lower oxides. Such an effect is not observed for the other studied metals. XPS measurement of the oxide targets confirms the formation of suboxides during ion bombardment as well as an oxygen deficient surface in the steady state. These effects are confirmed from the processing curves from the oxide targets showing an elevated sputtering rate in pure argon.

  7. Cellular Automata Modelling of Photo-Induced Oxidation Processes in Molecularly Doped Polymers

    Directory of Open Access Journals (Sweden)

    David M. Goldie

    2016-11-01

    Full Text Available The possibility of employing cellular automata (CA to model photo-induced oxidation processes in molecularly doped polymers is explored. It is demonstrated that the oxidation dynamics generated using CA models exhibit stretched-exponential behavior. This dynamical characteristic is in general agreement with an alternative analysis conducted using standard rate equations provided the molecular doping levels are sufficiently low to prohibit the presence of safe-sites which are impenetrable to dissolved oxygen. The CA models therefore offer the advantage of exploring the effect of dopant agglomeration which is difficult to assess from standard rate equation solutions. The influence of UV-induced bleaching or darkening upon the resulting oxidation dynamics may also be easily incorporated into the CA models and these optical effects are investigated for various photo-oxidation product scenarios. Output from the CA models is evaluated for experimental photo-oxidation data obtained from a series of hydrazone-doped polymers.

  8. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  9. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  10. Mass transfer model for two-layer TBP oxidation reactions

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

  11. Modelling of oxidation and hydriding behaviour of Zircaloy-2 pressure tubes in PHWR

    International Nuclear Information System (INIS)

    Sah, D.N.; Sunil Kumar; Khan, K.B.

    2002-01-01

    A computer model named DOCTOR (Deuteriding of Coolant Tubes during Operation of Reactor) has been developed for predicting the axial profile of oxide thickness and hydrogen (Deuterium) concentration in PHWR pressure tubes. This model is applicable to single channel or full core analysis. The main source of hydrogen is considered to be oxidation of pressure tube on the i.d. surface by high temperature coolant water. Three stages of oxidation is considered namely, pre- transition, post transition and accelerated. Oxidation rate is considered to be dependent on channel power, axial power/flux distribution, coolant temperature and pre-existing oxide thickness at the location. The kinetics parameters for oxidation model are derived from the actual measurement of oxide thickness on a number of pressure tubes examined in PIE Division. The input data required for the model are: channel power, channel power factor, axial flux distribution, coolant inlet temperature, critical oxide thickness, hydrogen pick up fraction, initial hydrogen in the material and time of operation (efpy). The model calculates the oxide layer thickness on the inside surface of the pressure tube along the length. The amount of hydrogen picked up by the pressure tube is calculated from the oxide thickness using hydrogen pick up fraction determined from the PIE data. The pressure tube length is divided into a number of axial segments for calculation. The temperature and fast neutron flux assumed to be constant in a given segment. The axial temperature profile calculated from the axial power profile in the channel is used for calculating the oxidation rate at various locations in the pressure tube. The model has been validated with PIE data of hydrogen equivalent measurement on a number of irradiated Zircaloy-2 pressure tubes of various PHWRs. The performance of the model in predicting the axial profile of hydrogen in the pressure tubes has been found to be good. (author)

  12. Impact of oxide thickness on gate capacitance – Modelling and ...

    Indian Academy of Sciences (India)

    Department of Electronics and Communication Engineering, National ... conventional HEMT, Schottky barrier diode is formed at the gate electrode. .... term corresponds to the energy required for the electric field in the oxide layer and the.

  13. Modelling the change in the oxidation coefficient during the aerobic ...

    African Journals Online (AJOL)

    2013-01-20

    Jan 20, 2013 ... activated sludge in batch reactors under different initial phenol concentrations. ... wet air oxidation, ozonation, non-catalytic, catalytic and ... design of aeration devices. ... using an open (flowing gas/static liquid) respirometer.

  14. Modelling nitrous oxide emissions from cropland at the regional scale

    Directory of Open Access Journals (Sweden)

    Gabrielle Benoît

    2006-11-01

    Full Text Available Arable soils are a large source of nitrous oxide (N2O emissions, making up half of the biogenic emissions worldwide. Estimating their source strength requires methods capable of capturing the spatial and temporal variability of N2O emissions, along with the effects of crop management. Here, we applied a process-based model, CERES, with geo-referenced input data on soils, weather, and land use to map N2O emissions from wheat-cropped soils in three agriculturally intensive regions in France. Emissions were mostly controlled by soil type and local climate conditions, and only to a minor extent by the doses of fertilizer nitrogen applied. As a result, the direct emission factors calculated at the regional level were much smaller (ranging from 0.0007 to 0.0033 kg N2O-N kg–1 N than the value of 0.0125 kg N2O-N kg–1 N currently recommended in the IPCC Tier 1 methodology. Regional emissions were far more sensitive to the soil microbiological parameter s governing denitrification and its fraction evolved as N2O, soil bulk density, and soil initial inorganic N content. Mitigation measures should therefore target a reduction in the amount of soil inorganic N upon sowing of winter crops, and a decrease of the soil N2O production potential itself. From a general perspective, taking into account the spatial variability of soils and climate thereby appears necessary to improve the accuracy of national inventories, and to tailor mitigation strategies to regional characteristics. The methodology and results presented here may easily be transferred to winter oilseed rape, whose has growing cycle and fertilser requirements are similar.

  15. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    Science.gov (United States)

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Behaviour of defective CANDU fuel: fuel oxidation kinetic and thermodynamic modelling

    International Nuclear Information System (INIS)

    Higgs, J.

    2005-01-01

    The thermal performance of operating CANDU fuel under defect conditions is affected by the ingress of heavy water into the fuel element. A mechanistic model has been developed to predict the extent of fuel oxidation in defective fuel and its affect on fuel thermal performance. A thermodynamic treatment of such oxidized fuel has been performed as a basis for the boundary conditions in the kinetic model. Both the kinetic and thermodynamic models have been benchmarked against recent experimental work. (author)

  17. Modeling Nitrous Oxide Production during Biological Nitrogen Removal via Nitrification and Denitrification: Extensions to the General ASM Models

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer i Nàcher, Carles

    2011-01-01

    on N2O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO2– participates as final electron acceptor compared to the oxic pathway. Among......Nitrous oxide (N2O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N2O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N2O...

  18. Unified computational model of transport in metal-insulating oxide-metal systems

    Science.gov (United States)

    Tierney, B. D.; Hjalmarson, H. P.; Jacobs-Gedrim, R. B.; Agarwal, Sapan; James, C. D.; Marinella, M. J.

    2018-04-01

    A unified physics-based model of electron transport in metal-insulator-metal (MIM) systems is presented. In this model, transport through metal-oxide interfaces occurs by electron tunneling between the metal electrodes and oxide defect states. Transport in the oxide bulk is dominated by hopping, modeled as a series of tunneling events that alter the electron occupancy of defect states. Electron transport in the oxide conduction band is treated by the drift-diffusion formalism and defect chemistry reactions link all the various transport mechanisms. It is shown that the current-limiting effect of the interface band offsets is a function of the defect vacancy concentration. These results provide insight into the underlying physical mechanisms of leakage currents in oxide-based capacitors and steady-state electron transport in resistive random access memory (ReRAM) MIM devices. Finally, an explanation of ReRAM bipolar switching behavior based on these results is proposed.

  19. Transient dynamic and modeling parameter sensitivity analysis of 1D solid oxide fuel cell model

    International Nuclear Information System (INIS)

    Huangfu, Yigeng; Gao, Fei; Abbas-Turki, Abdeljalil; Bouquain, David; Miraoui, Abdellatif

    2013-01-01

    Highlights: • A multiphysics, 1D, dynamic SOFC model is developed. • The presented model is validated experimentally in eight different operating conditions. • Electrochemical and thermal dynamic transient time expressions are given in explicit forms. • Parameter sensitivity is discussed for different semi-empirical parameters in the model. - Abstract: In this paper, a multiphysics solid oxide fuel cell (SOFC) dynamic model is developed by using a one dimensional (1D) modeling approach. The dynamic effects of double layer capacitance on the electrochemical domain and the dynamic effect of thermal capacity on thermal domain are thoroughly considered. The 1D approach allows the model to predict the non-uniform distributions of current density, gas pressure and temperature in SOFC during its operation. The developed model has been experimentally validated, under different conditions of temperature and gas pressure. Based on the proposed model, the explicit time constant expressions for different dynamic phenomena in SOFC have been given and discussed in detail. A parameters sensitivity study has also been performed and discussed by using statistical Multi Parameter Sensitivity Analysis (MPSA) method, in order to investigate the impact of parameters on the modeling accuracy

  20. Generalized kinetic model of reduction of molecular oxidant by metal containing redox

    International Nuclear Information System (INIS)

    Kravchenko, T.A.

    1986-01-01

    Present work is devoted to kinetics of reduction of molecular oxidant by metal containing redox. Constructed generalized kinetic model of redox process in the system solid redox - reagent solution allows to perform the general theoretical approach to research and to obtain new results on kinetics and mechanism of interaction of redox with oxidants.

  1. Experimental kinetic study and modeling of calcium oxide carbonation

    International Nuclear Information System (INIS)

    Rouchon, L.

    2012-01-01

    Anthropogenic carbon dioxide (CO 2 ) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO 2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO 2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO 2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/de-carbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO 2 , so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO 2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO 2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO 3 which causes a change in the

  2. Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

    International Nuclear Information System (INIS)

    Siefken, L.J.

    1999-01-01

    Models were designed to resolve deficiencies in the SCDAP/RELAP5/MOD3.2 calculations of the configuration and integrity of hot, partially oxidized cladding. These models are expected to improve the calculations of several important aspects of fuel rod behavior. First, an improved mapping was established from a compilation of PIE results from severe fuel damage tests of the configuration of melted metallic cladding that is retained by an oxide layer. The improved mapping accounts for the relocation of melted cladding in the circumferential direction. Then, rules based on PIE results were established for calculating the effect of cladding that has relocated from above on the oxidation and integrity of the lower intact cladding upon which it solidifies. Next, three different methods were identified for calculating the extent of dissolution of the oxidic part of the cladding due to its contact with the metallic part. The extent of dissolution effects the stress and thus the integrity of the oxidic part of the cladding. Then, an empirical equation was presented for calculating the stress in the oxidic part of the cladding and evaluating its integrity based on this calculated stress. This empirical equation replaces the current criterion for loss of integrity which is based on temperature and extent of oxidation. Finally, a new rule based on theoretical and experimental results was established for identifying the regions of a fuel rod with oxidation of both the inside and outside surfaces of the cladding. The implementation of these models is expected to eliminate the tendency of the SCDAP/RELAP5 code to overpredict the extent of oxidation of the upper part of fuel rods and to underpredict the extent of oxidation of the lower part of fuel rods and the part with a high concentration of relocated material. This report is a revision and reissue of the report entitled, Improvements in Modeling of Cladding Oxidation and Meltdown

  3. Metal Oxide Nanomaterial QNAR Models: Available Structural Descriptors and Understanding of Toxicity Mechanisms

    Directory of Open Access Journals (Sweden)

    Jiali Ying

    2015-10-01

    Full Text Available Metal oxide nanomaterials are widely used in various areas; however, the divergent published toxicology data makes it difficult to determine whether there is a risk associated with exposure to metal oxide nanomaterials. The application of quantitative structure activity relationship (QSAR modeling in metal oxide nanomaterials toxicity studies can reduce the need for time-consuming and resource-intensive nanotoxicity tests. The nanostructure and inorganic composition of metal oxide nanomaterials makes this approach different from classical QSAR study; this review lists and classifies some structural descriptors, such as size, cation charge, and band gap energy, in recent metal oxide nanomaterials quantitative nanostructure activity relationship (QNAR studies and discusses the mechanism of metal oxide nanomaterials toxicity based on these descriptors and traditional nanotoxicity tests.

  4. Models for solid oxide fuel cell systems exploitation of models hierarchy for industrial design of control and diagnosis strategies

    CERN Document Server

    Marra, Dario; Polverino, Pierpaolo; Sorrentino, Marco

    2016-01-01

    This book presents methodologies for optimal design of control and diagnosis strategies for Solid Oxide Fuel Cell systems. A key feature of the methodologies presented is the exploitation of modelling tools that balance accuracy and computational burden.

  5. Three model systems measure oxidation/nitration damage caused ...

    Indian Academy of Sciences (India)

    Unknown

    caused by peroxynitrite ... (OONO–) or its carbon dioxide derivatives cause oxidation/nitration and hence mutation to various body poly- mers e.g. .... The work described in this paper is quite brief due to ex- ... exact way to balance the dose of antioxidants in mixtures ... tralizing conditions the half-life of OONO– is less than.

  6. Ammonia-oxidizing bacteria: A model for molecular microbial ecology

    NARCIS (Netherlands)

    Kowalchuk, G.A.; Stephen, J.R.

    2001-01-01

    The eutrophication of many ecosystems in recent decades has led to an increased interest in the ecology of nitrogen transformation. Chemolitho-autotrophic ammonia-oxidizing bacteria are responsible for the rate-limiting step of nitrification in a wide variety of environments, making them important

  7. Ab Initio Thermodynamic Modeling of Electrified Metal-Oxide Interfaces

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Hansen, Martin Hangaard; Greeley, Jeff

    2015-01-01

    Solid oxide fuel cells are attractive devices in a sustainable energy context because of their fuel flexibility and potentially highly efficient conversion of chemical to electrical energy. The performance of the device is to a large extent determined by the atomic structure of the electrode-elec...

  8. Oxidation Phenomena in Advanced High Strength Steels : Modelling and Experiment

    NARCIS (Netherlands)

    Mao, W.

    2018-01-01

    Galvanized advanced high strength steels (AHSS) will be the most competitive structural material for automotive applications in the next decade. Oxidation of AHSS during the recrystalization annealing process in a continuous galvanizing line to a large extent influences the quality of zinc coating

  9. Employing RADIANCE to refine indoor photocatalytic oxidation modeling

    NARCIS (Netherlands)

    Pelzers, R.S.; Yu, Q.; Mangkuto, R.A.; Brouwers, H.J.H.

    2013-01-01

    Indoor air quality (IAQ) gained great attention in the last years as one of the foremost environmental concerns and it is therefore imperative that effective methods are developed to conserve IAQ. Currently, the novel technology photocatalytic oxidation (PCO) is a potential alternative. A

  10. Pulmonary oxidative stress, inflammation and dysregulated iron homeostatis in rat models of cardiovascular disease

    Science.gov (United States)

    Underlying cardiovascular disease (CVD) is considered a risk factor for the exacerbation of air pollution health effects. Therefore, rodent models of CVD are increasingly used to examine mechanisms ofvariation in susceptibility. Pulmonary oxidative stress, inflammation and altere...

  11. Modelling ionising radiation induced defect generation in bipolar oxides with gated diodes

    International Nuclear Information System (INIS)

    Barnaby, H.J.; Cirba, C.; Schrimpf, R.D.; Kosier, St.; Fouillat, P.; Montagner, X.

    1999-01-01

    Radiation-induced oxide defects that degrade electrical characteristics of bipolar junction transistor (BJTs) can be measured with the use of gated diodes. The buildup of defects and their effect on device radiation response are modeled with computer simulation. (authors)

  12. A mathematical model of bacteria capable of complete oxidation of ammonium predicts improved nitrogen removal and reduced production of nitrous oxide

    OpenAIRE

    Pokhilko, Alexandra; Ebenhöh, Oliver

    2017-01-01

    The removal of excess nutrients\\ud from water ecosystems requires oxidation of toxic\\ud ammonium by two types of bacteria; one oxidizes\\ud ammonium to nitrite and the other oxidizes nitrite\\ud to nitrate. The oxidation of ammonium is often\\ud incomplete and nitrite accumulates. Nitrite is also\\ud toxic, and is converted by the ammoniumoxidizing\\ud bacteria to nitrous oxide, a powerful\\ud greenhouse gas. Here we use mathematical\\ud modeling to analyze a potential solution to the\\ud problems re...

  13. Inhibition of oxidation in nuclear graphite

    International Nuclear Information System (INIS)

    Winston, Philip L.; Sterbentz, James W.; Windes, William E.

    2015-01-01

    Graphite is a fundamental material of high-temperature gas-cooled nuclear reactors, providing both structure and neutron moderation. Its high thermal conductivity, chemical inertness, thermal heat capacity, and high thermal structural stability under normal and off-normal conditions contribute to the inherent safety of these reactor designs. One of the primary safety issues for a high-temperature graphite reactor core is the possibility of rapid oxidation of the carbon structure during an off-normal design basis event where an oxidising atmosphere (air ingress) can be introduced to the hot core. Although the current Generation IV high-temperature reactor designs attempt to mitigate any damage caused by a postulated air ingress event, the use of graphite components that inhibit oxidation is a logical step to increase the safety of these reactors. Recent experimental studies of graphite containing between 5.5 and 7 wt% boron carbide (B 4 C) indicate that oxidation is dramatically reduced even at prolonged exposures at temperatures up to 900 deg. C. The proposed addition of B 4 C to graphite components in the nuclear core would necessarily be enriched in B-11 isotope in order to minimise B-10 neutron absorption and graphite swelling. The enriched boron can be added to the graphite during billet fabrication. Experimental oxidation rate results and potential applications for borated graphite in nuclear reactor components will be discussed. (authors)

  14. Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

    International Nuclear Information System (INIS)

    Mahieu, Koenraad; De Visscher, Alex; Vanrolleghem, Peter A.; Van Cleemput, Oswald

    2008-01-01

    A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between 12 CH 4 , 13 CH 4 , and 12 CH 3 D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per mille in the δ 13 C value, with δ 13 C the relative 13 C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods

  15. Mathematical Modelling to Predict Oxidative Behaviour of Conjugated Linoleic Acid in the Food Processing Industry

    Directory of Open Access Journals (Sweden)

    Aitziber Ojanguren

    2013-06-01

    Full Text Available Industrial processes that apply high temperatures in the presence of oxygen may compromise the stability of conjugated linoleic acid (CLA bioactive isomers. Statistical techniques are used in this study to model and predict, on a laboratory scale, the oxidative behaviour of oil with high CLA content, controlling the limiting factors of food processing. This modelling aims to estimate the impact of an industrial frying process (140 °C, 7 L/h air on the oxidation of CLA oil for use as frying oil instead of sunflower oil. A factorial design was constructed within a temperature (80–200 °C and air flow (7–20 L/h range. Oil stability index (Rancimat method was used as a measure of oxidation. Three-level full factorial design was used to obtain a quadratic model for CLA oil, enabling the oxidative behaviour to be predicted under predetermined process conditions (temperature and air flow. It is deduced that temperatures applied in food processes affect the oxidation of CLA to a greater extent than air flow. As a result, it is estimated that the oxidative stability of CLA oil is less resistant to industrial frying than sunflower oil. In conclusion, thanks to the mathematical model, a good choice of the appropriate industrial food process can be selected to avoid the oxidation of the bioactive isomers of CLA, ensuring its functionality in novel applications.

  16. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  17. Molecular modeling studies of oleate adsorption on iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Rath, Swagat S. [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Sinha, Nishant [Accelrys K.K, Bengaluru (India); Sahoo, Hrushikesh [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Das, Bisweswar, E-mail: bdas@immt.res.in [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Mishra, Barada Kanta [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India)

    2014-03-01

    Graphical abstract: - Highlights: • Plane wave periodic DFT study of oleate-iron oxide interaction. • Magnetite-oleate complex is more stable than hematite and goethite. • Flotation recovery of magnetite is more compared to the other two oxides. - Abstract: Comparative studies of oleate interaction with hematite, magnetite and goethite using density functional calculations are presented. The approach is illustrated by carrying out geometric optimization of oleate on the stable and most exposed planes of hematite, magnetite, and goethite. Interaction energies for oleate-mineral surface have been determined, based on which, magnetite is found to be forming the most stable complex with oleate. Trend as obtained from the quantum chemical calculations has been validated by contact angle measurements and flotation studies on hematite, magnetite and goethite with sodium oleate at different pH and collector concentrations.

  18. Molecular modeling studies of oleate adsorption on iron oxides

    International Nuclear Information System (INIS)

    Rath, Swagat S.; Sinha, Nishant; Sahoo, Hrushikesh; Das, Bisweswar; Mishra, Barada Kanta

    2014-01-01

    Graphical abstract: - Highlights: • Plane wave periodic DFT study of oleate-iron oxide interaction. • Magnetite-oleate complex is more stable than hematite and goethite. • Flotation recovery of magnetite is more compared to the other two oxides. - Abstract: Comparative studies of oleate interaction with hematite, magnetite and goethite using density functional calculations are presented. The approach is illustrated by carrying out geometric optimization of oleate on the stable and most exposed planes of hematite, magnetite, and goethite. Interaction energies for oleate-mineral surface have been determined, based on which, magnetite is found to be forming the most stable complex with oleate. Trend as obtained from the quantum chemical calculations has been validated by contact angle measurements and flotation studies on hematite, magnetite and goethite with sodium oleate at different pH and collector concentrations

  19. Mathematical Modeling of Wastewater Oxidation under Microgravity Conditions

    OpenAIRE

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

    2005-01-01

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

  20. Pineapple Waste Extract for Preventing Oxidation in Model Food Systems.

    Science.gov (United States)

    Segovia Gómez, Francisco; Almajano Pablos, María Pilar

    2016-07-01

    Pineapple (Ananas comosus) is consumed in the form of chunks (canned), cubes, fruit salad, and also in juices, concentrates, and jams. In the processes to produce these products, the waste generated represents a high percentage of the total fruit. Some studies have shown that residues of certain fruits, such as pineapple, have the same antioxidant activity as the fruit pulp. So although these residues are discarded, they could be used as an alternative source of polyphenols, as natural antioxidants. This study is focused on the antioxidant activity of wastes obtained in the production of pineapple products and their application. The polyphenols' scavenging activity was determined by the oxygen radical antioxidant capacity assay. The antioxidant potential was determined in emulsions (o/w) and in muffins, where the primary oxidation products (by peroxide value, PV) and the secondary oxidation products (by thiobarbituric acid reactive substances) were analyzed. In addition the muffins were analyzed by means of a triangular sensory test. The PV method showed that pineapple waste extracts caused a reduction in oxidation products of 59% in emulsions and 91% in the muffins. The reduction in TBARs values for emulsions were 27% and for muffins were 51%. The triangular sensory test showed that the samples containing the extract were not distinguished from the control (α = 0.05). © 2016 Institute of Food Technologists®

  1. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-08-01

    Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

  2. Numerical modelling of emissions of nitrogen oxides in solid fuel combustion.

    Science.gov (United States)

    Bešenić, Tibor; Mikulčić, Hrvoje; Vujanović, Milan; Duić, Neven

    2018-06-01

    Among the combustion products, nitrogen oxides are one of the main contributors to a negative impact on the environment, participating in harmful processes such as tropospheric ozone and acid rains production. The main source of emissions of nitrogen oxides is the human combustion of fossil fuels. Their formation models are investigated and implemented with the goal of obtaining a tool for studying the nitrogen-containing pollutant production. In this work, numerical simulation of solid fuel combustion was carried out on a three-dimensional model of a drop tube furnace by using the commercial software FIRE. It was used for simulating turbulent fluid flow and temperature field, concentrations of the reactants and products, as well as the fluid-particles interaction by numerically solving the integro-differential equations describing these processes. Chemical reactions mechanisms for the formation of nitrogen oxides were implemented by the user functions. To achieve reasonable calculation times for running the simulations, as well as efficient coupling with the turbulent mixing process, the nitrogen scheme is limited to sufficiently few homogeneous reactions and species. Turbulent fluctuations that affect the reaction rates of nitrogen oxides' concentration are modelled by probability density function approach. Results of the implemented model for nitrogen oxides' formation from coal and biomass are compared to the experimental data. Temperature, burnout and nitrogen oxides' concentration profiles are compared, showing satisfactory agreement. The new model allows the simulation of pollutant formation in the real-world applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Cladding oxidation during air ingress. Part II: Synthesis of modelling results

    International Nuclear Information System (INIS)

    Beuzet, E.; Haurais, F.; Bals, C.; Coindreau, O.; Fernandez-Moguel, L.; Vasiliev, A.; Park, S.

    2016-01-01

    Highlights: • A state-of-the-art for air oxidation modelling in the frame of severe accident is done. • Air oxidation models from main severe accident codes are detailed. • Simulations from main severe accident codes are compared against experimental results. • Perspectives in terms of need for further model development and experiments are given. - Abstract: Air ingress is a potential risk in some low probable situations of severe accidents in a nuclear power plant. Air is a highly oxidizing atmosphere that can lead to an enhanced Zr-based cladding oxidation and core degradation affecting the release of fission products. This is particularly true speaking about ruthenium release, due to its high radiotoxicity and its ability to form highly volatile oxides in a significant manner in presence of air. The oxygen affinity is decreasing from the Zircaloy cladding, fuel and ruthenium inclusions. It is consequently of great need to understand the phenomena governing cladding oxidation by air as a prerequisite for the source term issues in such scenarios. In the past years, many works have been done on cladding oxidation by air under severe accident conditions. This paper with in addition the paper “Cladding oxidation during air ingress – Part I: Synthesis of experimental results” of this journal issue aim at assessing the state of the art on this phenomenon. In this paper, the modelling of air ingress phenomena in the main severe accident codes (ASTEC, ATHLET-CD, MAAP, MELCOR, RELAP/SCDAPSIM, SOCRAT) is described in details, as well as the validation against the integral experiments QUENCH-10, QUENCH-16 and PARAMETER-SF4. A full review of cladding oxidation by air is thus established.

  4. Fatty acid oxidation changes and the correlation with oxidative stress in different preeclampsia-like mouse models.

    Directory of Open Access Journals (Sweden)

    Xiaoyan Ding

    Full Text Available BACKGROUND: Long-chain 3-hydroxyacyl-CoA dehydrogenase (LCHAD expression is decreased in placenta of some cases of preeclampsia (PE which may result in free fatty acid (FFA increased. High FFA level will induce oxidative stress, so abnormal long-chain fatty acid-oxidation may participate in the pathogenesis of PE through oxidative stress pathway. METHODS: PE-like groups were ApoC3 transgenic mice with abnormal fatty acid metabolism, classical PE-like models with injection of Nw-nitro-L-arginine-methyl ester (L-NA or lipopolysaccharide (LPS and the antiphospholipid syndrome (APS mouse model with β2GPI injection (ApoC3+NS, ApoC3+L-NA, L-NA, LPS and β2GPI groups. The control group was wild-type mice with normal saline injection. Except for β2GPI mice, the other mice were subdivided into pre-implantation (Pre and mid-pregnancy (Mid subgroups by injection time. RESULTS: All PE-like groups showed hypertension and proteinuria except ApoC3+NS mice only showed hypertension. Serum FFA levels increased significantly except in LPS group compared to controls (P<0.05. LCHAD mRNA and protein expression in the liver and placenta was significantly higher for ApoC3+NS, ApoC3+L-NA and β2GPI mice and lower for L-NA mice than controls (P<0.05 but did not differ between LPS mice and controls. P47phox mRNA and protein expression in the liver significantly increased in all PE-like groups except LPS group, while P47phox expression in the placenta only significantly increased in L-NA and β2GPI groups. CONCLUSIONS: Abnormal long-chain fatty acid-oxidation may play a different role in different PE-like models and in some cases participate in the pathogenesis of PE through oxidative stress pathway.

  5. Development of 3D Oxide Fuel Mechanics Models

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B. W. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Casagranda, A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pitts, S. A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, W. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2017-07-27

    This report documents recent work to improve the accuracy and robustness of the mechanical constitutive models used in the BISON fuel performance code. These developments include migration of the fuel mechanics models to be based on the MOOSE Tensor Mechanics module, improving the robustness of the smeared cracking model, implementing a capability to limit the time step size based on material model response, and improving the robustness of the return mapping iterations used in creep and plasticity models.

  6. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M

    2002-01-01

    The molten salts M2S2O7 and MHSO4, the binary molten salt Systems M2S2O7-MHSO4 and the molten salt-gas systems M2S2O7 V2O5 and M2S2O7-M2SO4 V2O5 (M = Na, K, Rb, Cs) in O-2, SO2 and At atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  7. A model for oxidizing species concentrations in boiling water reactors

    International Nuclear Information System (INIS)

    Sun, B.; Chexal, B.; Pathania, R.; Chun, J.; Ballinger, R.; Abdollahian, D.

    1993-01-01

    To evaluate and control the intergranular stress corrosion cracking of boiling water reactor (BWR) vessel internal components requires knowledge of the concentration of oxidizing species that affects the electrochemical potentials in various regions of a BWR. In a BWR flow circuit, as water flows through the radiation field, the radiolysis process and chemical reactions lead to the production of species such as oxygen, hydrogen, and hydrogen peroxide. Since chemistry measurements are difficult inside BWRs, analytical tools have been developed by Ruiz and Lin, Ibe and Uchida and Chun and Ballinger for estimating the concentration of species that provide the necessary input for water chemistry control and material protection

  8. Preparation and investigation of Al–4 wt % B4C nanocomposite ...

    Indian Academy of Sciences (India)

    cal behaviour including light weight, electrical and thermal conductivity (Boey et ... cle sizes, density, geometries, flow or the development of an electrical charge ... 2. Experimental. Argon gas atomized Al–2 wt % Cu powders with a mean size.

  9. Optimizing Grain Boundary Complexions to Produce Dense Pressure-Less Sintered Boron Carbide (B4C)

    Science.gov (United States)

    2008-11-14

    discontinuous distribution of the yttria. At this stage it is difficult to determine if the discontinuity is genuine or results from dewetting upon cooling...sample. However, the tendency of the film to form beads indicates a dewetting behavior. The weak interface between the yttria and the boron carbide...conform to the dewetting behavior. There is a possibility of a complexion transition as the sample is cooled down in the furnace. At high temperature the

  10. Grazing incidence Fe-line telescopes using W/B4C multilayers

    DEFF Research Database (Denmark)

    Joensen, Karsten D.; Gorenstein, Paul; Christensen, Finn Erland

    1994-01-01

    Traditional high-Z coated X-ray telescopes for the >= 1 keV range all have a loss of throughput with higher energies, owing to the inverse proportionality between the critical angle and energy. We have shown that this can, to some degree, be countered by employing multilayers on the outermost....... Depending on the specifics of the design, a factor 3 - 5 increased throughput was obtained in a narrow energy band, or a 30 - 100% increase in a wider-band. This throughput ia gained at the expense of the throughput at 2 - 4 keV, which is reduced by 20 - 30%....

  11. Wetting and interface phenomena in the B4C/(Cu-B-Si) system

    International Nuclear Information System (INIS)

    Aizenshtein, M.; Froumin, N.; Shapiro-Tsoref, E.; Dariel, M.P.; Frage, N.

    2005-01-01

    The addition of Si to a Cu-B liquid alloy improves wetting of the boron carbide substrate and allows maintaining a flat metal/ceramic interface. Improved wetting is associated with a shift of the boron content in the near surface layer of the substrate towards a higher B/C ratio. The experimental results are consistent with the thermodynamic analysis of the Cu-B-C-Si system

  12. Processing and microstructural characterization of B4C-Al cermets

    International Nuclear Information System (INIS)

    Halverson, D.C.; Pyzik, A.J.; Aksay, I.A.

    1985-01-01

    Reaction thermodynamics and wetting studies were employed to evaluate boron carbide-aluminum cermets. Wetting phonomenon and interfacial reactions are characterized using ''macroscale'' and ''microscale'' techniques. Macroscale evaluation involved aluminium sessile drop studies on boron carbide substrates. Microscale evaluation involved the fabrication of actural cermet microstructures and their characterization through sem, x-ray diffraction, metallography, and electron microprobe. Contact-angle measurements and interfacial-reaction products are reported

  13. Combustion of Na2B4O7 + Mg + C to synthesis B4C powders

    International Nuclear Information System (INIS)

    Jiang Guojian; Xu Jiayue; Zhuang Hanrui; Li Wenlan

    2009-01-01

    Boron carbide powder was fabricated by combustion synthesis (CS) method directly from mixed powders of borax (Na 2 B 4 O 7 ), magnesium (Mg) and carbon. The adiabatic temperature of the combustion reaction of Na 2 B 4 O 7 + 6 Mg + C was calculated. The control of the reactions was achieved by selecting reactant composition, relative density of powder compact and gas pressure in CS reactor. The effects of these different influential factors on the composition and morphologies of combustion products were investigated. The results show that, it is advantageous for more Mg/Na 2 B 4 O 7 than stoichiometric ratio in Na 2 B 4 O 7 + Mg + C system and high atmosphere pressure in the CS reactor to increase the conversion degree of reactants to end product. The final product with the minimal impurities' content could be fabricated at appropriate relative density of powder compact. At last, boron carbide without impurities could be obtained after the acid enrichment and distilled water washing.

  14. Dynamic Modeling, Model-Based Control, and Optimization of Solid Oxide Fuel Cells

    Science.gov (United States)

    Spivey, Benjamin James

    2011-07-01

    Solid oxide fuel cells are a promising option for distributed stationary power generation that offers efficiencies ranging from 50% in stand-alone applications to greater than 80% in cogeneration. To advance SOFC technology for widespread market penetration, the SOFC should demonstrate improved cell lifetime and load-following capability. This work seeks to improve lifetime through dynamic analysis of critical lifetime variables and advanced control algorithms that permit load-following while remaining in a safe operating zone based on stress analysis. Control algorithms typically have addressed SOFC lifetime operability objectives using unconstrained, single-input-single-output control algorithms that minimize thermal transients. Existing SOFC controls research has not considered maximum radial thermal gradients or limits on absolute temperatures in the SOFC. In particular, as stress analysis demonstrates, the minimum cell temperature is the primary thermal stress driver in tubular SOFCs. This dissertation presents a dynamic, quasi-two-dimensional model for a high-temperature tubular SOFC combined with ejector and prereformer models. The model captures dynamics of critical thermal stress drivers and is used as the physical plant for closed-loop control simulations. A constrained, MIMO model predictive control algorithm is developed and applied to control the SOFC. Closed-loop control simulation results demonstrate effective load-following, constraint satisfaction for critical lifetime variables, and disturbance rejection. Nonlinear programming is applied to find the optimal SOFC size and steady-state operating conditions to minimize total system costs.

  15. Optical modeling of nickel-base alloys oxidized in pressurized water reactor

    Energy Technology Data Exchange (ETDEWEB)

    Clair, A. [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France); Foucault, M.; Calonne, O. [Areva ANP, Centre Technique Departement Corrosion-Chimie, 30 Bd de l' industrie, BP 181, 71205 Le Creusot (France); Finot, E., E-mail: Eric.Finot@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France)

    2012-10-01

    The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution-precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude-Lorentz model. A robust optical stratification model was determined using focused ion beam cross-section of thin foils examined by transmission electron microscopy. Dielectric constants of the inner oxide layer depleted in chromium were assimilated to those of the nickel thin film. The optical constants of both the spinels and extern layer were determined. - Highlights: Black-Right-Pointing-Pointer Spectroscopic ellipsometry of Ni-base alloy oxidation in pressurized water reactor Black-Right-Pointing-Pointer Measurements of the dielectric constants of the alloys Black-Right-Pointing-Pointer Optical simulation of the mixed oxidation process using a three stack model Black-Right-Pointing-Pointer Scattered crystallites cationic outer layer; linear Ni-gradient bottom layer Black-Right-Pointing-Pointer Determination of the refractive index of the spinel and the Cr{sub 2}O{sub 3} layers.

  16. Model simulating oxidation of Zircalot-4 at 400 (C in water vapor. Influence of thermal cycling and structure

    International Nuclear Information System (INIS)

    Garcia, Eduardo A.; Beranguer, G.

    1998-01-01

    This work gives a model simulating the oxidation of Zircaloy-4 in water vapor at 400 (C with different precipitates and granular sizes. The model combines diffusion with inter linked porosity, defining also an interface in the oxide separating phases of inter linked porosity from non inter linked porosity in the (PI/PnL) oxide, which spreads in a discrete way in time and is capable of reproducing kinetics of experimental oxidation

  17. The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

    Science.gov (United States)

    Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

    2017-09-28

    Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

  18. The Adsorption of Cd(II on Manganese Oxide Investigated by Batch and Modeling Techniques

    Directory of Open Access Journals (Sweden)

    Xiaoming Huang

    2017-09-01

    Full Text Available Manganese (Mn oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999. The adsorption of Cd(II on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd at low pH and inner-sphere surface complexation sites (SOCd+ and (SO2CdOH− species at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface.

  19. The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

    Science.gov (United States)

    Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

    2017-01-01

    Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

  20. Bisphenol A Induces Hepatotoxicity through Oxidative Stress in Rat Model

    Directory of Open Access Journals (Sweden)

    Zeinab K. Hassan

    2012-01-01

    Full Text Available Reactive oxygen species (ROS are cytotoxic agents that lead to significant oxidative damage. Bisphenol A (BPA is a contaminant with increasing exposure to it and exerts both toxic and estrogenic effects on mammalian cells. Due to limited information concerning the effect of BPA on liver, this study investigates whether BPA causes hepatotoxicity by induction of oxidative stress in liver. Rats were divided into five groups: The first four groups, BPA (0.1, 1, 10, 50 mg/kg/day were administrated orally to rats for four weeks. The fifth group was taken water with vehicle. The final body weights in the 0.1 mg group showed a significant decrease compared to control group. Significant decreased levels of reduced glutathione, superoxide dismutase, glutathione peroxidase, glutathione-S-transferase, glutathione reductase and catalase activity were found in the 50 mg BPA group compared to control groups. High dose of BPA (50 mg/kg significantly increased the biochemical levels of ALT, ALP and total bilirubin. BPA effect on the activity of antioxidant genes was confirmed by real time PCR in which the expression levels of these genes in liver tissue were significantly decrease compared to control. Data from this study demonstrate that BPA generate ROS and reduce the antioxidant gene expression that causes hepatotoxicity.

  1. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  2. Coordinated HArd Sphere Model (CHASM): A Simplified Model for Silicate and Oxide Liquids at Mantle Conditions

    Science.gov (United States)

    Wolf, A. S.; Asimow, P. D.; Stevenson, D. J.

    2013-12-01

    Recent first-principles theoretical calculations (Stixrude 2009) and experimental shock-wave investigations (Mosenfelder 2009) indicate that melting perovskite requires significantly less energy than previously thought, supporting the idea of a deep-mantle magma ocean early in Earth's history. The modern-day solid Earth is thus likely the result of crystallization from an early predominantly molten state, a process that is primarily controlled by the poorly understood behavior of silicate melts at extreme pressures and temperatures. Probing liquid thermodynamics at mantle conditions is difficult for both theory and experiment, and further challenges are posed by the large relevant compositional space including at least MgO, SiO2, and FeO. First-principles molecular dynamics has been used with great success to determine the high P-T properties of a small set of fixed composition silicate-oxide liquids including MgO (Karki 2006), SiO2 (Karki 2007), Mg2SiO4 (de Koker 2008), MgSiO3 (Stixrude 2005), and Fe2SiO4 (Ramo 2012). While extremely powerful, this approach has limitations including high computational cost, lower bounds on temperature due to relaxation constraints, as well as restrictions to length scales and time scales that are many orders of magnitude smaller than those relevant to the Earth or experimental methods. As a compliment to accurate first-principles calculations, we have developed the Coordinated HArd Sphere Model (CHASM). We extend the standard hard sphere mixture model, recently applied to silicate liquids by Jing (2011), by accounting for the range of oxygen coordination states available to liquid cations. Utilizing approximate analytic expressions for the hard sphere model, the method can predict complex liquid structure and thermodynamics while remaining computationally efficient. Requiring only minutes on standard desktop computers rather than months on supercomputers, the CHASM approach is well-suited to providing an approximate thermodynamic

  3. Hypoxia and oxidation levels of DNA and lipids in humans and animal experimental models

    DEFF Research Database (Denmark)

    Møller, Peter; Risom, Lotte; Lundby, Carsten

    2008-01-01

    The objective of this review was to evaluate the association between hypoxia and oxidative damage to DNA and lipids. Evaluation criteria encompassed specificity and validation status of the biomarkers, study design, strength of the association, dose-response relationship, biological plausibility......, analogous exposures, and effect modification by intervention. The collective interpretation indicates persuasive evidence from the studies in humans for an association between hypoxia and elevated levels of oxidative damage to DNA and lipids. The levels of oxidatively generated DNA lesions and lipid...... in subjects at high altitude. Most of the animal experimental models should be interpreted with caution because the assays for assessment of lipid peroxidation products have suboptimal validity....

  4. Oxidative Stress Associated with Neuronal Apoptosis in Experimental Models of Epilepsy

    Directory of Open Access Journals (Sweden)

    Marisela Méndez-Armenta

    2014-01-01

    Full Text Available Epilepsy is considered one of the most common neurological disorders worldwide. Oxidative stress produced by free radicals may play a role in the initiation and progression of epilepsy; the changes in the mitochondrial and the oxidative stress state can lead mechanism associated with neuronal death pathway. Bioenergetics state failure and impaired mitochondrial function include excessive free radical production with impaired synthesis of antioxidants. This review summarizes evidence that suggest what is the role of oxidative stress on induction of apoptosis in experimental models of epilepsy.

  5. Modeling and experimental evaluation of the diffusion bonding of the oxide dispersion strengthened steel PM2000

    International Nuclear Information System (INIS)

    Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

    2015-01-01

    A modeling based optimization process of the solid state diffusion bonding is presented for joining ferritic oxide dispersion strengthened steels PM2000. An optimization study employing varying bonding temperatures and pressures results in almost the same strength and toughness of the bonded compared to the as received material. TEM investigations of diffusion bonded samples show a homogeneous distribution of oxide particles at the bonding seam similar to that in the bulk. Hence, no loss in strength or creep resistance due to oxide particle agglomeration is found, as verified by the mechanical properties observed for the joint.

  6. Windows(Registered Trademark)-Based Software Models Cyclic Oxidation Behavior

    Science.gov (United States)

    Smialek, J. L.; Auping, J. V.

    2004-01-01

    Oxidation of high-temperature aerospace materials is a universal issue for combustion-path components in turbine or rocket engines. In addition to the question of the consumption of material due to growth of protective scale at use temperatures, there is also the question of cyclic effects and spallation of scale on cooldown. The spallation results in the removal of part of the protective oxide in a discontinuous step and thereby opens the way for more rapid oxidation upon reheating. In experiments, cyclic oxidation behavior is most commonly characterized by measuring changes in weight during extended time intervals that include hundreds or thousands of heating and cooling cycles. Weight gains occurring during isothermal scale-growth processes have been well characterized as being parabolic or nearly parabolic functions of time because diffusion controls reaction rates. In contrast, the net weight change in cyclic oxidation is the sum of the effects of the growth and spallation of scale. Typically, the net weight gain in cyclic oxidation is determined only empirically (that is, by measurement), with no unique or straightforward mathematical connection to either the rate of growth or the amount of metal consumed. Thus, there is a need for mathematical modeling to infer spallation mechanisms. COSP is a computer program that models the growth and spallation processes of cyclic oxidation on the basis of a few elementary assumptions that were discussed in COSP: A Computer Model of Cyclic Oxidation, Oxidation of Metals, vol. 36, numbers 1 and 2, 1991, pages 81-112. Inputs to the model include the selection of an oxidation-growth law and a spalling geometry, plus oxide-phase, growth-rate, cycle-duration, and spall-constant parameters. (The spalling fraction is often shown to be a constant factor times the existing amount of scale.) The output of COSP includes the net change in weight, the amounts of retained and spalled oxide, the total amounts of oxygen and metal

  7. Modelling of elementary kinetics of H2 and CO oxidation on ceria pattern cells

    International Nuclear Information System (INIS)

    Patel, HC; Tabish, AN; Aravind, PV

    2015-01-01

    Elementary kinetic mechanisms of fuel oxidation on ceria have not been dealt with in detail in literature. An elementary kinetic model is developed considering charge transfer and adsorption steps for electrochemical H 2 and CO oxidation on ceria. The reaction chemistry is solved by fitting previously obtained impedance spectra for H 2 and CO oxidation on ceria. The rate determining step is found to be the charge transfer rather than the adsorption for both H 2 and CO. A method is presented to extend the kinetics obtained from pattern anodes to macroscopic simulations in which the activation overvoltage can be calculated on the basis of elementary kinetics.

  8. Configurational Model for Conductivity of Stabilized Fluorite Structure Oxides

    DEFF Research Database (Denmark)

    Poulsen, Finn Willy

    1981-01-01

    The formalism developed here furnishes means by which ionic configurations, solid solution limits, and conductivity mechanisms in doped fluorite structures can be described. The present model differs markedly from previous models but reproduces qualitatively reality. The analysis reported...

  9. Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

    International Nuclear Information System (INIS)

    Merino, J.; Cera, E.; Bruno, J.; Quinones, J.; Casas, I.; Clarens, F.; Gimenez, J.; Pablo, J. de; Rovira, M.; Martinez-Esparza, A.

    2005-01-01

    Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2 , particularly the role of · OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions

  10. A simple model to estimate the optimal doping of p - Type oxide superconductors

    Directory of Open Access Journals (Sweden)

    Adir Moysés Luiz

    2008-12-01

    Full Text Available Oxygen doping of superconductors is discussed. Doping high-Tc superconductors with oxygen seems to be more efficient than other doping procedures. Using the assumption of double valence fluctuations, we present a simple model to estimate the optimal doping of p-type oxide superconductors. The experimental values of oxygen content for optimal doping of the most important p-type oxide superconductors can be accounted for adequately using this simple model. We expect that our simple model will encourage further experimental and theoretical researches in superconducting materials.

  11. Kinetic modeling of antimony(III) oxidation and sorption in soils.

    Science.gov (United States)

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-05

    Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Mathematical modelling of the kinetics of aerosol oxidation of sulfur dioxide upon electron-beam purification of power-plant flue gases from nitrogen and sulfur oxides

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Gerasimova, T.S.; Fadeev, S.A.

    1996-01-01

    A kinetic model of SO 2 oxidation in flue gases, irradiated with accelerated electron flux is proposed. The model comprises an optimized mechanism of gas phase radiation chemical oxidation of NO and SO 2 , kinetics circuit of SO 2 and NH 3 thermal interaction, kinetic models of volumetric condensation of water and sulfuric acid vapors and liquid-phase oxidation of SO 2 in aerosol drops, produced in the course of volumetric condensation. Calculation results are in a satisfactory agreement with experimental data. (author)

  13. Large-scale Modeling of Nitrous Oxide Production: Issues of Representing Spatial Heterogeneity

    Science.gov (United States)

    Morris, C. K.; Knighton, J.

    2017-12-01

    Nitrous oxide is produced from the biological processes of nitrification and denitrification in terrestrial environments and contributes to the greenhouse effect that warms Earth's climate. Large scale modeling can be used to determine how global rate of nitrous oxide production and consumption will shift under future climates. However, accurate modeling of nitrification and denitrification is made difficult by highly parameterized, nonlinear equations. Here we show that the representation of spatial heterogeneity in inputs, specifically soil moisture, causes inaccuracies in estimating the average nitrous oxide production in soils. We demonstrate that when soil moisture is averaged from a spatially heterogeneous surface, net nitrous oxide production is under predicted. We apply this general result in a test of a widely-used global land surface model, the Community Land Model v4.5. The challenges presented by nonlinear controls on nitrous oxide are highlighted here to provide a wider context to the problem of extraordinary denitrification losses in CLM. We hope that these findings will inform future researchers on the possibilities for model improvement of the global nitrogen cycle.

  14. Dynamic modelling of nitrous oxide emissions from three Swedish sludge liquor treatment systems

    DEFF Research Database (Denmark)

    Lindblom, E.; Arnell, M.; Flores-Alsina, X.

    2016-01-01

    The objective of this paper is to model the dynamics and validate the results of nitrous oxide (N2O)emissions from three Swedish nitrifying/denitrifying, nitritation and anammox systems treating real anaerobic digester sludge liquor. The Activated Sludge Model No. 1 is extended to describe N2O...

  15. Development of the kinetic model of platinum catalyzed ammonia oxidation in a microreactor

    NARCIS (Netherlands)

    Rebrov, E.V.; Croon, de M.H.J.M.; Schouten, J.C.

    2002-01-01

    The ammonia oxidation reaction on supported polycrystalline platinum catalyst was investigated in an aluminum-based microreactor. An extensive set of reactions was included in the chemical reactor modeling to facilitate the construction of a kinetic model capable of satisfactory predictions for a

  16. Three-phase boundary length in solid-oxide fuel cells: A mathematical model

    Science.gov (United States)

    Janardhanan, Vinod M.; Heuveline, Vincent; Deutschmann, Olaf

    A mathematical model to calculate the volume specific three-phase boundary length in the porous composite electrodes of solid-oxide fuel cell is presented. The model is exclusively based on geometrical considerations accounting for porosity, particle diameter, particle size distribution, and solids phase distribution. Results are presented for uniform particle size distribution as well as for non-uniform particle size distribution.

  17. Energy-Efficient and Environmentally Friendly Solid Oxide Membrane Electrolysis Process for Magnesium Oxide Reduction: Experiment and Modeling

    Science.gov (United States)

    Guan, Xiaofei; Pal, Uday B.; Powell, Adam C.

    2014-06-01

    This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM(La0.8Sr0.2MnO3-δ)-Inconel inert anode current collector for production of magnesium and oxygen directly from magnesium oxide at 1423 K (1150 °C). The electrochemical performance of the SOM cell was evaluated by means of various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scan, and electrolysis. Electronic transference numbers of the flux were measured to assess the magnesium dissolution in the flux during SOM electrolysis. The effects of magnesium solubility in the flux on the current efficiency and the SOM stability during electrolysis are discussed. An inverse correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed. Based on the experimental results, a new equivalent circuit of the SOM electrolysis process is presented. A general electrochemical polarization model of SOM process for magnesium and oxygen gas production is developed, and the maximum allowable applied potential to avoid zirconia dissociation is calculated as well. The modeling results suggest that a high electronic resistance of the flux and a relatively low electronic resistance of SOM are required to achieve membrane stability, high current efficiency, and high production rates of magnesium and oxygen.

  18. Modeling and parametric simulations of solid oxide fuel cells with methane carbon dioxide reforming

    International Nuclear Information System (INIS)

    Ni, Meng

    2013-01-01

    Highlights: ► A 2D model is developed for solid oxide fuel cells (SOFCs). ► CH 4 reforming by CO 2 (MCDR) is included. ► SOFC with MCDR shows comparable performance with methane steam reforming SOFC. ► Increasing CO electrochemical oxidation greatly enhances the SOFC performance. ► Effects of potential and temperature on SOFC performance are also discussed. - Abstract: A two-dimensional model is developed to simulate the performance of solid oxide fuel cells (SOFCs) fed with CO 2 and CH 4 mixture. The electrochemical oxidations of both CO and H 2 are included. Important chemical reactions are considered in the model, including methane carbon dioxide reforming (MCDR), reversible water gas shift reaction (WGSR), and methane steam reforming (MSR). It’s found that at a CH 4 /CO 2 molar ratio of 50/50, MCDR and reversible WGSR significantly influence the cell performance while MSR is negligibly small. The performance of SOFC fed with CO 2 /CH 4 mixture is comparable to SOFC running on CH 4 /H 2 O mixtures. The electric output of SOFC can be enhanced by operating the cell at a low operating potential or at a high temperature. In addition, the development of anode catalyst with high activity towards CO electrochemical oxidation is important for SOFC performance enhancement. The model can serve as a useful tool for optimization of the SOFC system running on CH 4 /CO 2 mixtures

  19. Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

    Science.gov (United States)

    Jachimowski, C. J.; Wilson, C. H.

    1980-01-01

    The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

  20. Computational Modeling of Cobalt-based Water Oxidation: Current Status and Future Challenges

    Science.gov (United States)

    Schilling, Mauro; Luber, Sandra

    2018-04-01

    A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysis. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability towards real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

  1. Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges

    Directory of Open Access Journals (Sweden)

    Mauro Schilling

    2018-04-01

    Full Text Available A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

  2. Kinetic Modeling of a Heterogeneous Fenton Oxidative Treatment of Petroleum Refining Wastewater

    Science.gov (United States)

    Basheer Hasan, Diya'uddeen; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2014-01-01

    The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k 2′), their final oxidation step (k 1′), and the direct conversion to endproducts step (k 3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

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

    International Nuclear Information System (INIS)

    Malang, S.; Neitzel, H.J.

    1983-01-01

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

  4. Genome-Scale, Constraint-Based Modeling of Nitrogen Oxide Fluxes during Coculture of Nitrosomonas europaea and Nitrobacter winogradskyi

    Science.gov (United States)

    Giguere, Andrew T.; Murthy, Ganti S.; Bottomley, Peter J.; Sayavedra-Soto, Luis A.

    2018-01-01

    ABSTRACT Nitrification, the aerobic oxidation of ammonia to nitrate via nitrite, emits nitrogen (N) oxide gases (NO, NO2, and N2O), which are potentially hazardous compounds that contribute to global warming. To better understand the dynamics of nitrification-derived N oxide production, we conducted culturing experiments and used an integrative genome-scale, constraint-based approach to model N oxide gas sources and sinks during complete nitrification in an aerobic coculture of two model nitrifying bacteria, the ammonia-oxidizing bacterium Nitrosomonas europaea and the nitrite-oxidizing bacterium Nitrobacter winogradskyi. The model includes biotic genome-scale metabolic models (iFC578 and iFC579) for each nitrifier and abiotic N oxide reactions. Modeling suggested both biotic and abiotic reactions are important sources and sinks of N oxides, particularly under microaerobic conditions predicted to occur in coculture. In particular, integrative modeling suggested that previous models might have underestimated gross NO production during nitrification due to not taking into account its rapid oxidation in both aqueous and gas phases. The integrative model may be found at https://github.com/chaplenf/microBiome-v2.1. IMPORTANCE Modern agriculture is sustained by application of inorganic nitrogen (N) fertilizer in the form of ammonium (NH4+). Up to 60% of NH4+-based fertilizer can be lost through leaching of nitrifier-derived nitrate (NO3−), and through the emission of N oxide gases (i.e., nitric oxide [NO], N dioxide [NO2], and nitrous oxide [N2O] gases), the latter being a potent greenhouse gas. Our approach to modeling of nitrification suggests that both biotic and abiotic mechanisms function as important sources and sinks of N oxides during microaerobic conditions and that previous models might have underestimated gross NO production during nitrification. PMID:29577088

  5. Genome-Scale, Constraint-Based Modeling of Nitrogen Oxide Fluxes during Coculture of Nitrosomonas europaea and Nitrobacter winogradskyi.

    Science.gov (United States)

    Mellbye, Brett L; Giguere, Andrew T; Murthy, Ganti S; Bottomley, Peter J; Sayavedra-Soto, Luis A; Chaplen, Frank W R

    2018-01-01

    Nitrification, the aerobic oxidation of ammonia to nitrate via nitrite, emits nitrogen (N) oxide gases (NO, NO 2 , and N 2 O), which are potentially hazardous compounds that contribute to global warming. To better understand the dynamics of nitrification-derived N oxide production, we conducted culturing experiments and used an integrative genome-scale, constraint-based approach to model N oxide gas sources and sinks during complete nitrification in an aerobic coculture of two model nitrifying bacteria, the ammonia-oxidizing bacterium Nitrosomonas europaea and the nitrite-oxidizing bacterium Nitrobacter winogradskyi . The model includes biotic genome-scale metabolic models (iFC578 and iFC579) for each nitrifier and abiotic N oxide reactions. Modeling suggested both biotic and abiotic reactions are important sources and sinks of N oxides, particularly under microaerobic conditions predicted to occur in coculture. In particular, integrative modeling suggested that previous models might have underestimated gross NO production during nitrification due to not taking into account its rapid oxidation in both aqueous and gas phases. The integrative model may be found at https://github.com/chaplenf/microBiome-v2.1. IMPORTANCE Modern agriculture is sustained by application of inorganic nitrogen (N) fertilizer in the form of ammonium (NH 4 + ). Up to 60% of NH 4 + -based fertilizer can be lost through leaching of nitrifier-derived nitrate (NO 3 - ), and through the emission of N oxide gases (i.e., nitric oxide [NO], N dioxide [NO 2 ], and nitrous oxide [N 2 O] gases), the latter being a potent greenhouse gas. Our approach to modeling of nitrification suggests that both biotic and abiotic mechanisms function as important sources and sinks of N oxides during microaerobic conditions and that previous models might have underestimated gross NO production during nitrification.

  6. Modeling of thermo-mechanical and irradiation behavior of mixed oxide fuel for sodium fast reactors

    International Nuclear Information System (INIS)

    Karahan, Aydin; Buongiorno, Jacopo

    2010-01-01

    An engineering code to model the irradiation behavior of UO 2 -PuO 2 mixed oxide fuel pins in sodium-cooled fast reactors was developed. The code was named fuel engineering and structural analysis tool (FEAST-OXIDE). FEAST-OXIDE has several modules working in coupled form with an explicit numerical algorithm. These modules describe: (1) fission gas release and swelling, (2) fuel chemistry and restructuring, (3) temperature distribution, (4) fuel-clad chemical interaction and (5) fuel-clad mechanical analysis. Given the fuel pin geometry, composition and irradiation history, FEAST-OXIDE can analyze fuel and cladding thermo-mechanical behavior at both steady-state and design-basis transient scenarios. The code was written in FORTRAN-90 program language. The mechanical analysis module implements the LIFE algorithm. Fission gas release and swelling behavior is described by the OGRES and NEFIG models. However, the original OGRES model has been extended to include the effects of joint oxide gain (JOG) formation on fission gas release and swelling. A detailed fuel chemistry model has been included to describe the cesium radial migration and JOG formation, oxygen and plutonium radial distribution and the axial migration of cesium. The fuel restructuring model includes the effects of as-fabricated porosity migration, irradiation-induced fuel densification, grain growth, hot pressing and fuel cracking and relocation. Finally, a kinetics model is included to predict the clad wastage formation. FEAST-OXIDE predictions have been compared to the available FFTF, EBR-II and JOYO databases, as well as the LIFE-4 code predictions. The agreement was found to be satisfactory for steady-state and slow-ramp over-power accidents.

  7. Modeling of thermo-mechanical and irradiation behavior of mixed oxide fuel for sodium fast reactors

    Energy Technology Data Exchange (ETDEWEB)

    Karahan, Aydin, E-mail: karahan@mit.ed [Center for Advanced Nuclear Energy Systems, Nuclear Science and Engineering Department, Massachusetts Institute of Technology, MA (United States); Buongiorno, Jacopo [Center for Advanced Nuclear Energy Systems, Nuclear Science and Engineering Department, Massachusetts Institute of Technology, MA (United States)

    2010-01-31

    An engineering code to model the irradiation behavior of UO{sub 2}-PuO{sub 2} mixed oxide fuel pins in sodium-cooled fast reactors was developed. The code was named fuel engineering and structural analysis tool (FEAST-OXIDE). FEAST-OXIDE has several modules working in coupled form with an explicit numerical algorithm. These modules describe: (1) fission gas release and swelling, (2) fuel chemistry and restructuring, (3) temperature distribution, (4) fuel-clad chemical interaction and (5) fuel-clad mechanical analysis. Given the fuel pin geometry, composition and irradiation history, FEAST-OXIDE can analyze fuel and cladding thermo-mechanical behavior at both steady-state and design-basis transient scenarios. The code was written in FORTRAN-90 program language. The mechanical analysis module implements the LIFE algorithm. Fission gas release and swelling behavior is described by the OGRES and NEFIG models. However, the original OGRES model has been extended to include the effects of joint oxide gain (JOG) formation on fission gas release and swelling. A detailed fuel chemistry model has been included to describe the cesium radial migration and JOG formation, oxygen and plutonium radial distribution and the axial migration of cesium. The fuel restructuring model includes the effects of as-fabricated porosity migration, irradiation-induced fuel densification, grain growth, hot pressing and fuel cracking and relocation. Finally, a kinetics model is included to predict the clad wastage formation. FEAST-OXIDE predictions have been compared to the available FFTF, EBR-II and JOYO databases, as well as the LIFE-4 code predictions. The agreement was found to be satisfactory for steady-state and slow-ramp over-power accidents.

  8. Oxidative Damage and Cellular Defense Mechanisms in Sea Urchin Models of Aging

    Science.gov (United States)

    Du, Colin; Anderson, Arielle; Lortie, Mae; Parsons, Rachel; Bodnar, Andrea

    2013-01-01

    The free radical or oxidative stress theory of aging proposes that the accumulation of oxidative cellular damage is a major contributor to the aging process and a key determinant of species longevity. This study investigates the oxidative stress theory in a novel model for aging research, the sea urchin. Sea urchins present a unique model for the study of aging due to the existence of species with tremendously different natural life spans including some species with extraordinary longevity and negligible senescence. Cellular oxidative damage, antioxidant capacity and proteasome enzyme activities were measured in the tissues of three sea urchin species: short-lived Lytechinus variegatus, long-lived Strongylocentrotus franciscanus and Strongylocentrotus purpuratus which has an intermediate lifespan. Levels of protein carbonyls and 4-hydroxynonenal (HNE) measured in tissues (muscle, nerve, esophagus, gonad, coelomocytes, ampullae) and 8-hydroxy-2’-deoxyguanosine (8-OHdG) measured in cell-free coelomic fluid showed no general increase with age. The fluorescent age-pigment lipofuscin measured in muscle, nerve and esophagus, increased with age however it appeared to be predominantly extracellular. Antioxidant mechanisms (total antioxidant capacity, superoxide dismutase) and proteasome enzyme activities were maintained with age. In some instances, levels of oxidative damage were lower and antioxidant activity higher in cells or tissues of the long-lived species compared to the short-lived species, however further studies are required to determine the relationship between oxidative damage and longevity in these animals. Consistent with the predictions of the oxidative stress theory of aging, the results suggest that negligible senescence is accompanied by a lack of accumulation of cellular oxidative damage with age and maintenance of antioxidant capacity and proteasome enzyme activities may be important mechanisms to mitigate damage. PMID:23707327

  9. Plutonium chemistry: a synthesis of experimental data and a quantitative model for plutonium oxide solubility

    International Nuclear Information System (INIS)

    Haschke, J.M.; Oversby, V.M.

    2002-01-01

    The chemistry of plutonium is important for assessing potential behavior of radioactive waste under conditions of geologic disposal. This paper reviews experimental data on dissolution of plutonium oxide solids, describes a hybrid kinetic-equilibrium model for predicting steady-state Pu concentrations, and compares laboratory results with predicted Pu concentrations and oxidation-state distributions. The model is based on oxidation of PuO 2 by water to produce PuO 2+x , an oxide that can release Pu(V) to solution. Kinetic relationships between formation of PuO 2+x , dissolution of Pu(V), disproportionation of Pu(V) to Pu(IV) and Pu(VI), and reduction of Pu(VI) are given and used in model calculations. Data from tests of pyrochemical salt wastes in brines are discussed and interpreted using the conceptual model. Essential data for quantitative modeling at conditions relevant to nuclear waste repositories are identified and laboratory experiments to determine rate constants for use in the model are discussed

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  11. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.; Dagaut, P.; Togbé , Casimir; Dayma, Guillaume; Sarathy, Mani; Westbrook, Charles K.; Egolfopoulos, Fokion N.

    2013-01-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  12. Generalized first-order kinetic model for biosolids decomposition and oxidation during hydrothermal treatment.

    Science.gov (United States)

    Shanableh, A

    2005-01-01

    The main objective of this study was to develop generalized first-order kinetic models to represent hydrothermal decomposition and oxidation of biosolids within a wide range of temperatures (200-450 degrees C). A lumping approach was used in which oxidation of the various organic ingredients was characterized by the chemical oxygen demand (COD), and decomposition was characterized by the particulate (i.e., nonfilterable) chemical oxygen demand (PCOD). Using the Arrhenius equation (k = k(o)e(-Ea/RT)), activation energy (Ea) levels were derived from 42 continuous-flow hydrothermal treatment experiments conducted at temperatures in the range of 200-450 degrees C. Using predetermined values for k(o) in the Arrhenius equation, the activation energies of the various organic ingredients were separated into 42 values for oxidation and a similar number for decomposition. The activation energy values were then classified into levels representing the relative ease at which the organic ingredients of the biosolids were oxidized or decomposed. The resulting simple first-order kinetic models adequately represented, within the experimental data range, hydrothermal decomposition of the organic particles as measured by PCOD and oxidation of the organic content as measured by COD. The modeling approach presented in the paper provide a simple and general framework suitable for assessing the relative reaction rates of the various organic ingredients of biosolids.

  13. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.

    2013-09-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  14. A Holistic Model That Physicochemically Links Iron Oxide - Apatite and Iron Oxide - Copper - Gold Deposits to Magmas

    Science.gov (United States)

    Simon, A. C.; Reich, M.; Knipping, J.; Bilenker, L.; Barra, F.; Deditius, A.; Lundstrom, C.; Bindeman, I. N.

    2015-12-01

    Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and

  15. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander; Sarathy, Mani; Curran, Henry J.; Davis, Alexander C.; Westbrook, Charles K.; Pitz, William J.

    2012-01-01

    To help overcome the world's dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  16. Electrochemical Impedance Modeling of a Solid Oxide Fuel Cell Anode

    DEFF Research Database (Denmark)

    Mohammadi, R.; Søgaard, Martin; Ramos, Tania

    2014-01-01

    (TLM), which is suitably modified to account for the electrode microstructural details, is used for modeling the impedance arising from the electrochemical reactions. In order to solve the system of nonlinear equations, an in-house code based on the finite difference method was developed. Some...

  17. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  18. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  19. Mathematical modeling of nitrous oxide production in an anaerobic/oxic/anoxic process.

    Science.gov (United States)

    Ding, Xiaoqian; Zhao, Jianqiang; Hu, Bo; Chen, Ying; Ge, Guanghuan; Li, Xiaoling; Wang, Sha; Gao, Kun; Tian, Xiaolei

    2016-12-01

    This study incorporates three currently known nitrous oxide (N 2 O) production pathways: ammonium-oxidizing bacteria (AOB) denitrification, incomplete hydroxylamine (NH 2 OH) oxidation, and heterotrophic denitrification on intracellular polymers, into a mathematical model to describe N 2 O production in an anaerobic/oxic/anoxic (AOA) process for the first time. The developed model was calibrated and validated by four experimental cases, then evaluated by two independent anaerobic/aerobic (AO) studies from literature. The modeling results displayed good agreement with the measured data. N 2 O was primarily generated in the aerobic stage by AOB denitrification (67.84-81.64%) in the AOA system. Smaller amounts of N 2 O were produced via incomplete NH 2 OH oxidation (15.61-32.17%) and heterotrophic denitrification on intracellular polymers (0-12.47%). The high nitrite inhibition on N 2 O reductase led to the increased N 2 O accumulation in heterotrophic denitrification on intracellular polymers. The new model was capable of modeling nitrification-denitrification dynamics and heterotrophic denitrification on intracellular polymers in the AOA system. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Optimization of operating conditions in oxidation of dibenzothiophene in the light hydrocarbon model

    Directory of Open Access Journals (Sweden)

    Akbari Azam

    2014-01-01

    Full Text Available In this research, the effects of process variables on the efficiency and mechanism of dibenzothiophene oxidation in formicacid/H2O2 system for deep desulfurization of a light hydrocarbon model were systematically studied by statistical modelling and optimization using response surface methodology and implementing the central composite design. A quadratic regression model was developed to predict the yield of sulfur oxidation as the model response. The model indicated that temperature was the most significant effective factor and suggested an important interaction between temperature and H2O2/sulfur ratio; at temperatures above 56°C, more excess oxidant was necessary because of instability of active peroxo intermediates and loss of H2O2 due to thermal decomposition. In contrast, the water hindrance effect of H2O2 aqueous solution in desulfurization progress was more significant at temperatures bellow 56°C. In the optimization process, minimizing H2O2/sulfur ratio and catalyst consumption for maximum yield of desulfurization was economically considerable. The optimal condition was obtained at temperature of 57 °C, H2O2/sulfur ratio of 2.5 mol/mol and catalyst dosage of 0.82 mL in 50 mL solution of DBT in n-hexane leading to a maximum oxidation yield of 95% after 1 hour reaction. Good agreement between predicted and experimental results (less than 4% error was found.

  1. Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

    International Nuclear Information System (INIS)

    Crist, K.C.

    1984-10-01

    An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables

  2. Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

    Energy Technology Data Exchange (ETDEWEB)

    Crist, K.C.

    1984-10-01

    An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables.

  3. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    International Nuclear Information System (INIS)

    Swaminathan, Srinivasan; Spiegel, Michael

    2007-01-01

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N 2 -5% H 2 gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal

  4. Chemometrics models for assessment of oxidative stress risk in chrome-electroplating workers.

    Science.gov (United States)

    Zendehdel, Rezvan; Shetab-Boushehri, Seyed Vahid; Azari, Mansoor R; Hosseini, Vajihe; Mohammadi, Hamidreza

    2015-04-01

    Oxidative stress is the main cause of hexavalant chromium-induced damage in chrome electroplating workers. The main goal of this study is toxicity analysis and the possibility of toxicity risk categorizing in the chrome electroplating workers based on oxidative stress parameters as prognostic variables. We assessed blood chromium levels and biomarkers of oxidative stress such as lipid peroxidation, thiol (SH) groups and antioxidant capacity of plasma. Data were subjected to principle component analysis (PCA) and artificial neuronal network (ANN) to obtain oxidative stress pattern for chrome electroplating workers. Blood chromium levels increased from 4.42 ppb to 10.6 ppb. Induction of oxidative stress was observed by increased in lipid peroxidation (22.38 ± 10.47 μM versus 14.74 ± 4.82 μM, p chrome electroplaters. The result showed multivariate modeling can be interpreted as the induced biochemical toxicity in the workers exposed to hexavalent chromium. Different occupation groups were assessed on the basis of risk level of oxidative stress which could further justify proceeding engineering control measures.

  5. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, Srinivasan [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)]. E-mail: s.swaminathan@mpie.de; Spiegel, Michael [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)

    2007-03-15

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N{sub 2}-5% H{sub 2} gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal.

  6. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Model for solid oxide fuel cell cathodes prepared by infiltration

    DEFF Research Database (Denmark)

    Samson, Alfred Junio; Søgaard, Martin; Hendriksen, Peter Vang

    2017-01-01

    A 1-dimensional model of a cathode has been developed in order to understand and predict the performance of cathodes prepared by infiltration of La0.6Sr0.4Co1.05O3-δ (LSC) into porous backbones of Ce0.9Gd0.1O1.95 (CGO). The model accounts for the mixed ionic and electronic conductivity of LSC......, ionic conductivity of CGO, gas transport in the porous cathode, and the oxygen reduction reaction at the surface of percolated LSC. Geometrical variations are applied to reflect a changing microstructure of LSC under varying firing temperatures. Using microstructural parameters obtained from detailed...... scanning electron microscopy and simulations of the measured polarization resistances, an expression for the area specific resistance (rp) associated with the oxygen exchange on the surface of the infiltrated LSC particles was extracted and compared with literature values. A series of microstructural...

  8. Oxidation flow reactors (OFRs): overview of recent field and modeling studies

    Science.gov (United States)

    Jimenez, Jose-Luis; Palm, Brett B.; Peng, Zhe; Hu, Weiwei; Ortega, Amber M.; Li, Rui; Campuzano-Jost, Pedro; Day, Douglas A.; Stark, Harald; Brune, William H.; de Gouw, Joost; Schroder, Jason

    2016-04-01

    Oxidation flow reactors (OFRs) are popular tools for studying SOA formation and aging in both laboratory and field experiments. In an OFR, the concentration of an oxidant (OH, O3, or NO3) can be increased, leading to hours-months of equivalent atmospheric oxidation during the several-minute OFR residence time. Using gas- and particle-phase measurements from several recent field campaigns, we demonstrate SOA formation after oxidation of ambient air in an OFR. Typically, more SOA formation is observed from nighttime air than daytime air. This indicates that the concentration of SOA-forming gases in ambient air is relatively higher at night. Measured ambient VOCs are not able to explain the magnitude of SOA formation in the OFR, suggesting that typically unmeasured S/IVOCs (possibly VOC oxidation products or direct emissions) play a substantial intermediary role in ambient SOA formation. We also present highlights from recent OFR oxidant chemistry modeling studies. HOx, Ox, and photolysis chemistry was modeled for two common OH production methods (utilizing 185+254 nm UV light, or 254 nm only). OH exposure (OHexp) can be estimated within a factor of ~2 using model-derived equations, and can be verified in situ using VOC decay measurements. OHexp is strongly dependent on external OH reactivity, which may cause significant OH suppression in some circumstances (e.g., lab/source studies with high precursor concentrations). UV light photolysis and reaction with oxygen atoms are typically not major reaction pathways. Modeling the fate of condensable low-volatility organic gases (LVOCs) formed in an OFR suggests that LVOC fate is dependent on particle condensational sink. E.g., for the range of particle condensational sink at a remote pine forest, anywhere from 20-80% of produced LVOCs were predicted to condense onto aerosols for an OHexp of ~1 day, with the remainder lost to OFR or sampling line walls. Similar to large chamber wall loss corrections, a correction is needed

  9. Numerical modeling of nitrogen oxide emission and experimental verification

    Directory of Open Access Journals (Sweden)

    Szecowka Lech

    2003-12-01

    Full Text Available The results of nitrogen reduction in combustion process with application of primary method are presented in paper. The reduction of NOx emission, by the recirculation of combustion gasses, staging of fuel and of air was investigated, and than the reduction of NOx emission by simultaneous usage of the mentioned above primary method with pulsatory disturbances.The investigations contain numerical modeling of NOx reduction and experimental verification of obtained numerical calculation results.

  10. Mitochondrial Alterations and Oxidative Stress in an Acute Transient Mouse Model of Muscle Degeneration

    Science.gov (United States)

    Ramadasan-Nair, Renjini; Gayathri, Narayanappa; Mishra, Sudha; Sunitha, Balaraju; Mythri, Rajeswara Babu; Nalini, Atchayaram; Subbannayya, Yashwanth; Harsha, Hindalahalli Chandregowda; Kolthur-Seetharam, Ullas; Bharath, Muchukunte Mukunda Srinivas

    2014-01-01

    Muscular dystrophies (MDs) and inflammatory myopathies (IMs) are debilitating skeletal muscle disorders characterized by common pathological events including myodegeneration and inflammation. However, an experimental model representing both muscle pathologies and displaying most of the distinctive markers has not been characterized. We investigated the cardiotoxin (CTX)-mediated transient acute mouse model of muscle degeneration and compared the cardinal features with human MDs and IMs. The CTX model displayed degeneration, apoptosis, inflammation, loss of sarcolemmal complexes, sarcolemmal disruption, and ultrastructural changes characteristic of human MDs and IMs. Cell death caused by CTX involved calcium influx and mitochondrial damage both in murine C2C12 muscle cells and in mice. Mitochondrial proteomic analysis at the initial phase of degeneration in the model detected lowered expression of 80 mitochondrial proteins including subunits of respiratory complexes, ATP machinery, fatty acid metabolism, and Krebs cycle, which further decreased in expression during the peak degenerative phase. The mass spectrometry (MS) data were supported by enzyme assays, Western blot, and histochemistry. The CTX model also displayed markers of oxidative stress and a lowered glutathione reduced/oxidized ratio (GSH/GSSG) similar to MDs, human myopathies, and neurogenic atrophies. MS analysis identified 6 unique oxidized proteins from Duchenne muscular dystrophy samples (n = 6) (versus controls; n = 6), including two mitochondrial proteins. Interestingly, these mitochondrial proteins were down-regulated in the CTX model thereby linking oxidative stress and mitochondrial dysfunction. We conclude that mitochondrial alterations and oxidative damage significantly contribute to CTX-mediated muscle pathology with implications for human muscle diseases. PMID:24220031

  11. Endothelin receptor antagonist attenuates oxidative stress in a neonatal sepsis piglet model.

    Science.gov (United States)

    Goto, Tatenobu; Hussein, Mohamed Hamed; Kato, Shin; Daoud, Ghada Abdel-Hamid; Kato, Takenori; Sugiura, Takahiro; Kakita, Hiroki; Nobata, Masanori; Kamei, Michi; Mizuno, Haruo; Imai, Masaki; Ito, Tetsuya; Kato, Ineko; Suzuki, Satoshi; Okada, Noriko; Togari, Hajime; Okada, Hidechika

    2012-12-01

    Oxidative stress (oxidant-antioxidant imbalance) plays an important role in the pathophysiology of neonatal sepsis. This study evaluated whether an antisense peptide endothelin receptor antagonist, ETR-P1/fl, could attenuate oxidative stress in a neonatal sepsis model. A total of 18 3-d-old piglets were anesthetized and mechanically ventilated. Six piglets received cecal ligation and perforation (CLP group) for induction of sepsis. Six piglets also received continuous infusion (0.05 mg/kg/h) of ETR-P1/fl 30 min after CLP (ETR-P1/fl group). Six piglets received a sham operation. Serum total hydroperoxide (TH), biological antioxidant potentials (BAPs), oxidative stress index (OSI, calculated as TH/BAP), interleukin (IL)-6, serum glutamic oxaloacetic transaminase (GOT), and creatinine were measured before CLP and at 1, 3, and 6 h after CLP. CLP evoked a state of shock resulting in elevated TH, OSI, and IL-6 levels. ETR-P1/fl administration after CLP resulted in lower serum TH at 1 and 3 h after CLP, OSI at 1 and 3 h after CLP, IL-6 at 1 and 3 h after CLP, and GOT at 3 and 6 h after CLP as compared with the CLP group. ETR-P1/fl treatment significantly attenuated the elevation of serum oxidative stress markers (TH and OSI), IL-6, and GOT in a progressive neonatal sepsis CLP model.

  12. Effects of Photobiomodulation Therapy on Oxidative Stress in Muscle Injury Animal Models: A Systematic Review

    Directory of Open Access Journals (Sweden)

    Solange Almeida dos Santos

    2017-01-01

    Full Text Available This systematic review was performed to identify the role of photobiomodulation therapy on experimental muscle injury models linked to induce oxidative stress. EMBASE, PubMed, and CINAHL were searched for studies published from January 2006 to January 2016 in the areas of laser and oxidative stress. Any animal model using photobiomodulation therapy to modulate oxidative stress was included in analysis. Eight studies were selected from 68 original articles targeted on laser irradiation and oxidative stress. Articles were critically assessed by two independent raters with a structured tool for rating the research quality. Although the small number of studies limits conclusions, the current literature indicates that photobiomodulation therapy can be an effective short-term approach to reduce oxidative stress markers (e.g., thiobarbituric acid-reactive and to increase antioxidant substances (e.g., catalase, glutathione peroxidase, and superoxide dismutase. However, there is a nonuniformity in the terminology used to describe the parameters and dose for low-level laser treatment.

  13. Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products

    Science.gov (United States)

    Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.

    2017-07-01

    Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

  14. NITROUS OXIDE EMISSIONS FROM SOUTHERN HIGH PLAINS BEEF CATTLE FEEDYARDS: MEASUREMENT AND MODELING

    Science.gov (United States)

    Predictive models for nitrous oxide emission are crucial for assessing the greenhouse gas footprint of beef cattle production. The Texas Panhandle produces approximately 42% of finished beef in the U.S. and cattle production is estimated to contribute 8 Tg carbon dioxide equivalents from nitrous oxi...

  15. Nitrous Oxide Production in a Granule-based Partial Nitritation Reactor: A Model-based Evaluation.

    Science.gov (United States)

    Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

    2017-04-03

    Sustainable wastewater treatment has been attracting increasing attentions over the past decades. However, the production of nitrous oxide (N 2 O), a potent GHG, from the energy-efficient granule-based autotrophic nitrogen removal is largely unknown. This study applied a previously established N 2 O model, which incorporated two N 2 O production pathways by ammonia-oxidizing bacteria (AOB) (AOB denitrification and the hydroxylamine (NH 2 OH) oxidation). The two-pathway model was used to describe N 2 O production from a granule-based partial nitritation (PN) reactor and provide insights into the N 2 O distribution inside granules. The model was evaluated by comparing simulation results with N 2 O monitoring profiles as well as isotopic measurement data from the PN reactor. The model demonstrated its good predictive ability against N 2 O dynamics and provided useful information about the shift of N 2 O production pathways inside granules for the first time. The simulation results indicated that the increase of oxygen concentration and granule size would significantly enhance N 2 O production. The results further revealed a linear relationship between N 2 O production and ammonia oxidation rate (AOR) (R 2  = 0.99) under the conditions of varying oxygen levels and granule diameters, suggesting that bulk oxygen and granule size may exert an indirect effect on N 2 O production by causing a change in AOR.

  16. Characterization of subcritical water oxidation with in situ monitoring and self-modeling curve resolution

    International Nuclear Information System (INIS)

    Gemperline, Paul J.; Yang Yu; Bian Zhihui

    2003-01-01

    In this paper, a subcritical water oxidation (SBWO) process was monitored using self-modeling curve resolution (SMCR) of in situ UV-Vis measurements to estimate time-dependant composition profiles of reactants, intermediates and products. A small laboratory scale reactor with UV-Vis fiber-optic probes and a flow cell was used to demonstrate the usefulness of SMCR for monitoring the destruction of model compounds phenol, benzoic acid, and aniline in a dilute aqueous solutions. Hydrogen peroxide was used as the oxidizing reagent at moderate temperature (150-250 deg. C) and pressure (60-90 atm) in a single phase. By use of in situ monitoring, reaction times were easily determined and conditions for efficient oxidations were easily diagnosed without the need for time consuming off-line reference measurements. For selected runs, the destruction of the model compound was confirmed by gas chromatography and chemical oxygen demand (COD) measurements. Suspected intermediate oxidation products were easily detected by the use of UV-Vis spectrometry and self-modeling curve resolution, but could not be detected by gas chromatography

  17. Designing efficient nitrous oxide sampling strategies in agroecosystems using simulation models

    Science.gov (United States)

    Debasish Saha; Armen R. Kemanian; Benjamin M. Rau; Paul R. Adler; Felipe Montes

    2017-01-01

    Annual cumulative soil nitrous oxide (N2O) emissions calculated from discrete chamber-based flux measurements have unknown uncertainty. We used outputs from simulations obtained with an agroecosystem model to design sampling strategies that yield accurate cumulative N2O flux estimates with a known uncertainty level. Daily soil N2O fluxes were simulated for Ames, IA (...

  18. Oxidative stress in a rat model of cotton smoke inhalation-induced ...

    African Journals Online (AJOL)

    Background: Smoke inhalation injury refers to airway and lung parenchyma injury and general chemical damage caused by inhaling toxic gases and substances. The aim of this study was to explore the oxidative stress mechanism of cotton smoke inhalation-induced pulmonary injury in a rat model. Materials and Methods: ...

  19. Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

    Science.gov (United States)

    Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

    2012-09-01

    The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

  20. Manipulation of nitric oxide in an animal model of acute liver injury ...

    African Journals Online (AJOL)

    We evaluated the impact of altering nitric oxide release on acute liver injury, the associated gut injury and bacterial translocation, at different time intervals. Methods: An acute rat liver injury model induced by D-galactosamine was used. Sprague Dawley rats were divided into four main groups: normal control, acute liver ...

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

    International Nuclear Information System (INIS)

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

    1991-07-01

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

  2. IMMORTALIZED MICROGLIAL CELLS AS A MODEL SYSTEM FOR OXIDATIVE STRESS: PESTICIDE-INDUCED GENOMIC GHANGES.

    Science.gov (United States)

    In risk assessment there is a need to accelerate toxicological evaluation of vast numbers of chemicals. New programs focus on identifying common modes of action and on model systems for rapid screening. In this study we address both these issues. Oxidative stress is a good can...

  3. Modeling low-dose-rate effects in irradiated bipolar-base oxides

    International Nuclear Information System (INIS)

    Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F.; Michez, A.; Fleetwood, D.M.; Witczak, S.C.

    1997-02-01

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in BJTs. Simulations show that space charge limited transport is partially responsible for the low-dose-rate enhancement

  4. Selective cleavage of the C(α)-C(β) linkage in lignin model compounds via Baeyer-Villiger oxidation.

    Science.gov (United States)

    Patil, Nikhil D; Yao, Soledad G; Meier, Mark S; Mobley, Justin K; Crocker, Mark

    2015-03-21

    Lignin is an amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective oxidation of benzylic hydroxyl groups, followed by Baeyer-Villiger oxidation of the resulting ketones, successfully cleaves the Cα-Cβ linkage in these model compounds.

  5. Development and Validation of a Mathematical Model for Olive Oil Oxidation

    Science.gov (United States)

    Rahmouni, K.; Bouhafa, H.; Hamdi, S.

    2009-03-01

    A mathematical model describing the stability or the susceptibility to oxidation of extra virgin olive oil has been developed. The model has been resolved by an iterative method using differential finite method. It was validated by experimental data of extra virgin olive oil (EVOO) oxidation. EVOO stability was tested by using a Rancimat at four different temperatures 60, 70, 80 and 90° C until peroxide accumulation reached 20 [meq/kg]. Peroxide formation is speed relatively slow; fits zero order reaction with linear regression coefficients varying from 0, 98 to 0, 99. The mathematical model was used to predict the shelf life of bulk conditioned olive oil. This model described peroxide accumulation inside a container in excess of oxygen as a function of time at various positions from the interface air/oil. Good correlations were obtained between theoretical and experimental values.

  6. Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

    Directory of Open Access Journals (Sweden)

    Linxu Chen

    Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

  7. Modeling and Structural Optimization of Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Panagakos, Grigorios

    energy basket of solutions. In this project, consulting role was also undertaken by researchers at National Center for Sustainable Energy, Risø and more specifically by Dr. Martin Søgaard, Dr. Henrik Frandsen and Dr. Peter Vang Hendriksen (team leader). The other approach is based on attacking......, such as the tortuosity and the porosity of the material, for preselected micro-structures. Furthermore, we apply optimization techniques to lead this ASR to minimization. This work has been the fruit of collaboration with Professor Sossina Haile at the California Institute of Technology (Caltech) and with assistant...... Professor Francesco Ciucci at the Hong Kong University of Science and Technology (HKUST). As a complementary in this modeling work, we have also developed other activities, leading to either already accepted, submitted or soon to be submitted publications. These additional to the main focus directions, have...

  8. Oxidative stress contributes to outcome severity in a Drosophila melanogaster model of classic galactosemia

    Directory of Open Access Journals (Sweden)

    Patricia P. Jumbo-Lucioni

    2013-01-01

    Classic galactosemia is a genetic disorder that results from profound loss of galactose-1P-uridylyltransferase (GALT. Affected infants experience a rapid escalation of potentially lethal acute symptoms following exposure to milk. Dietary restriction of galactose prevents or resolves the acute sequelae; however, many patients experience profound long-term complications. Despite decades of research, the mechanisms that underlie pathophysiology in classic galactosemia remain unclear. Recently, we developed a Drosophila melanogaster model of classic galactosemia and demonstrated that, like patients, GALT-null Drosophila succumb in development if exposed to galactose but live if maintained on a galactose-restricted diet. Prior models of experimental galactosemia have implicated a possible association between galactose exposure and oxidative stress. Here we describe application of our fly genetic model of galactosemia to the question of whether oxidative stress contributes to the acute galactose sensitivity of GALT-null animals. Our first approach tested the impact of pro- and antioxidant food supplements on the survival of GALT-null and control larvae. We observed a clear pattern: the oxidants paraquat and DMSO each had a negative impact on the survival of mutant but not control animals exposed to galactose, and the antioxidants vitamin C and α-mangostin each had the opposite effect. Biochemical markers also confirmed that galactose and paraquat synergistically increased oxidative stress on all cohorts tested but, interestingly, the mutant animals showed a decreased response relative to controls. Finally, we tested the expression levels of two transcripts responsive to oxidative stress, GSTD6 and GSTE7, in mutant and control larvae exposed to galactose and found that both genes were induced, one by more than 40-fold. Combined, these results implicate oxidative stress and response as contributing factors in the acute galactose sensitivity of GALT-null Drosophila and, by

  9. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Science.gov (United States)

    Lima-Cabello, Elena; Garcia-Guirado, Francisco; Calvo-Medina, Rocio; el Bekay, Rajaa; Perez-Costillas, Lucia; Quintero-Navarro, Carolina; Sanchez-Salido, Lourdes

    2016-01-01

    Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome. PMID:26788253

  10. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Directory of Open Access Journals (Sweden)

    Elena Lima-Cabello

    2016-01-01

    Full Text Available Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome.

  11. Modeling nitrous oxide production during biological nitrogen removal via nitrification and denitrification: extensions to the general ASM models.

    Science.gov (United States)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer-Nàcher, Carles; Smets, Barth F

    2011-09-15

    Nitrous oxide (N(2)O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N(2)O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N(2)O dynamics during both nitrification and denitrification in biological N removal. Six additional processes and three additional reactants, all involved in known biochemical reactions, have been added. The validity and applicability of the model is demonstrated by comparing simulations with experimental data on N(2)O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO(2)(-) participates as final electron acceptor compared to the oxic pathway. Among the four denitrification steps, the last one (N(2)O reduction to N(2)) seems to be inhibited first when O(2) is present. Overall, N(2)O production can account for 0.1-25% of the consumed N in different nitrification and denitrification systems, which can be well simulated by the proposed model. In conclusion, we provide a modeling structure, which adequately captures N(2)O dynamics in autotrophic nitrification and heterotrophic denitrification driven biological N removal processes and which can form the basis for ongoing refinements.

  12. Three-phase boundary length in solid-oxide fuel cells: A mathematical model

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, Vinod M. [Institutefor Chemical Technology and Polymer Chemistry, University of Karlsruhe (TH), Kaiserstr. 12, D-76128 Karlsruhe (Germany); Heuveline, Vincent; Deutschmann, Olaf [Institute for Applied and Numerical Mathematics, University of Karlsruhe (TH), Kaiserstr. 12, D-76128 Karlsruhe (Germany)

    2008-03-15

    A mathematical model to calculate the volume specific three-phase boundary length in the porous composite electrodes of solid-oxide fuel cell is presented. The model is exclusively based on geometrical considerations accounting for porosity, particle diameter, particle size distribution, and solids phase distribution. Results are presented for uniform particle size distribution as well as for non-uniform particle size distribution. (author)

  13. Optimization of a model of red blood cells for the study of anti-oxidant drugs, in terms of concentration of oxidant and phosphate buffer.

    Science.gov (United States)

    Bureau, A; Lahet, J-J; Lenfant, F; Bouyer, F; Petitjean, M; Chaillot, B; Freysz, M

    2005-08-01

    The aggression of erythrocytes by an oxidative stress induces hemolysis. This paper aims to valid a model of erythrocytes in terms of composition of the phosphate buffer solution and of concentration of a well-known oxidant, AAPH. Three compositions of phosphate buffer solution are mixed with three concentrations of oxidant. The influence of these two parameters on hemolysis is independently studied by a variance analysis and a Kruskal-Wallis test when ANOVA is not available. The hemolysis rate increases with time at fixed oxidant concentration, but is not influenced by the composition of the buffer solution. The highest hemolysis rate, 90%, was only measured within 2 h with the highest oxidant concentration. If we retain this concentration of oxidant, the lower concentration of the buffer can by eliminated by a significant less hemolysis and the highest concentration of the buffer can by chosen in regard of the better precision for a similar hemolysis compared to the mean buffer. We hope to study the effect of anti-oxidant agent with such a model of erythrocytes.

  14. Modelling of Leakage Current Through Double Dielectric Gate Stack in Metal Oxide Semiconductor Capacitor

    International Nuclear Information System (INIS)

    Fatimah A Noor; Mikrajuddin Abdullah; Sukirno; Khairurrijal

    2008-01-01

    In this paper, we have derived analytical expression of leakage current through double barriers in Metal Oxide Semiconductor (MOS) capacitor. Initially, electron transmittance through the MOS capacitor was derived by including the coupling between the transverse and longitudinal energies. The transmittance was then employed to obtain leakage current through the double barrier. In this model, we observed the effect of electron velocity due to the coupling effect and the oxide thickness to the leakage current. The calculated results showed that the leakage current decreases as the electron velocity increases. (author)

  15. A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

    Science.gov (United States)

    Chen, Lin; Yueming, Li

    2018-06-01

    In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

  16. Modelling of nitrogen oxides distribution in the hearth of gas-fired industrial furnace

    Science.gov (United States)

    Zhubrin, S.; Glazov, V.; Guzhov, S.

    2017-11-01

    A model is proposed for calculating the formation and transportation of nitrogen oxides in the combustion chamber of an industrial furnace heated by gaseous fuels burning. The calculations use a three-dimensional stationary description of turbulent flow and mixing of fuel and oxidizer flows in the presence of heat transfer, mass transfer, and momentum between them transfer. Simulation of the spatial pattern of nitrogen oxides formation in the working space of the furnace is performed in the programming and computing suite SCAN. It is shown that the temperature non-uniformity over the hearth surface is not too pronounced due to the organization of the inclined flow inlet in the direction of the hearth, which is a desirable feature of the furnace operation. The highest concentration of combustion products is observed in the zone of maximum temperatures. In addition, the existence of two zones of the highest generation of oxides has been determined. The first zone is located approximately in the center of the hearth, and the second is located on the far external surface of the furnace. The possibility of using the developed model in the SCAN complex for carrying out parametric studies and engineering calculations, as well as for modification in the direction of adjusting and adapting the model to the regime-constructive features of specific energy technological devices, is noted.

  17. Thymoquinone Attenuates Brain Injury via an Anti-oxidative Pathway in a Status Epilepticus Rat Model.

    Science.gov (United States)

    Shao, Yi-Ye; Li, Bing; Huang, Yong-Mei; Luo, Qiong; Xie, Yang-Mei; Chen, Ying-Hui

    2017-01-01

    Status epilepticus (SE) results in the generation of reactive oxygen species (ROS), which contribute to seizure-induced brain injury. It is well known that oxidative stress plays a pivotal role in status epilepticus (SE). Thymoquinone (TQ) is a bioactive monomer extracted from black cumin (Nigella sativa) seed oil that has anti-inflammatory, anti-cancer, and antioxidant activity in various diseases. This study evaluated the protective effects of TQ on brain injury in a lithium-pilocarpine rat model of SE and investigated the underlying mechanism related to antioxidative pathway. Electroencephalogram and Racine scale were used to value seizure severity. Passive-avoidance test was used to determine learning and memory function. Moreover, anti-oxidative activity of TQ was observed using Western blot and super oxide dismutase (SOD) activity assay. Latency to SE increased in the TQ-pretreated group compared with rats in the model group, while the total power was significantly lower. Seizure severity measured on the Racine scale was significantly lower in the TQ group compared with the model group. Results of behavioral experiments suggest that TQ may also have a protective effect on learning and memory function. Investigation of the protective mechanism of TQ showed that TQ-pretreatment significantly increased the expression of Nrf2, HO-1 proteins and SOD in the hippocampus. These findings showed that TQ attenuated brain injury induced by SE via an anti-oxidative pathway.

  18. Identification of total reversible cysteine oxidation in an atherosclerosis model using a modified biotin switch assay.

    Science.gov (United States)

    Li, Ru; Huang, Jiqing; Kast, Juergen

    2015-05-01

    Oxidative stress due to the imbalance of reactive oxygen species (ROS) and the resulting reversible cysteine oxidation (CysOX) are involved in the early proatherogenic aspect of atherosclerosis. Given that the corresponding redox signaling pathways are still unclear, a modified biotin switch assay was developed to quantify the reversible CysOX in an atherosclerosis model established by using a monocytic cell line treated with platelet releasate. The accumulation of ROS was observed in the model system and validated in human primary monocytes. Through the application of the modified biotin switch assay, we obtained the first reversible CysOX proteome for this model. A total of 75 peptides, corresponding to 53 proteins, were quantified with oxidative modification. The bioinformatics analysis of these CysOX-containing proteins highlighted biological processes including glycolysis, cytoskeleton arrangement, and redox regulation. Moreover, the reversible oxidation of three glycolysis enzymes was observed using this method, and the regulation influence was verified by an enzyme activity assay. NADPH oxidase (NOX) inhibition treatment, in conjunction with the modified biotin switch method, was used to evaluate the global CysOX status. In conclusion, this versatile modified biotin switch assay provides an approach for the quantification of all reversible CysOX and for the study of redox signaling in atherosclerosis as well as in diseases in other biological systems.

  19. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  20. Catalytic oxidation using nitrous oxide

    Directory of Open Access Journals (Sweden)

    Juan Carlos Beltran-Prieto

    2017-01-01

    Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

  1. Oxidation of organics in water in microfluidic electrochemical reactors: Theoretical model and experiments

    International Nuclear Information System (INIS)

    Scialdone, Onofrio; Guarisco, Chiara; Galia, Alessandro

    2011-01-01

    The electrochemical oxidation of organics in water performed in micro reactors on boron doped diamond (BDD) anode was investigated both theoretically and experimentally in order to find the influence of various operative parameters on the conversion and the current efficiency CE of the process. The electrochemical oxidation of formic acid (FA) was selected as a model case. High conversions for a single passage of the electrolytic solution inside the cell were obtained by operating with proper residence times and low distances between cathode and anode. The effect of initial concentration, flow rate and current density was investigated in detail. Theoretical predictions were in very good agreement with experimental results for both mass transfer control, oxidation reaction control and mixed kinetic regimes in spite of the fact that no adjustable parameters was used. Mass transfer process was successfully modelled by considering for simplicity a constant Sh number (e.g., a constant mass transfer coefficient k m ) for a process performed with no high values of the current intensity to minimize the effect of the gas bubbling on the flowdynamic pattern. For mixed kinetic regimes, two different modelling approaches were used. In the first one, the oxidation of organics at BDD was assumed to be mass transfer controlled and to occur with an intrinsic 100% CE when applied current density is higher than the limiting current density. In the second case, the CE of the process was modelled assuming that the competition between organic and water oxidation depends only on the electrodic material and on the nature and the concentration of the organic. In the latter case a better agreement between experimental data and theoretical predictions was observed.

  2. First-principles calculations of orientation dependence of Si thermal oxidation based on Si emission model

    Science.gov (United States)

    Nagura, Takuya; Kawachi, Shingo; Chokawa, Kenta; Shirakawa, Hiroki; Araidai, Masaaki; Kageshima, Hiroyuki; Endoh, Tetsuo; Shiraishi, Kenji

    2018-04-01

    It is expected that the off-state leakage current of MOSFETs can be reduced by employing vertical body channel MOSFETs (V-MOSFETs). However, in fabricating these devices, the structure of the Si pillars sometimes cannot be maintained during oxidation, since Si atoms sometimes disappear from the Si/oxide interface (Si missing). Thus, in this study, we used first-principles calculations based on the density functional theory, and investigated the Si emission behavior at the various interfaces on the basis of the Si emission model including its atomistic structure and dependence on Si crystal orientation. The results show that the order in which Si atoms are more likely to be emitted during thermal oxidation is (111) > (110) > (310) > (100). Moreover, the emission of Si atoms is enhanced as the compressive strain increases. Therefore, the emission of Si atoms occurs more easily in V-MOSFETs than in planar MOSFETs. To reduce Si missing in V-MOSFETs, oxidation processes that induce less strain, such as wet or pyrogenic oxidation, are necessary.

  3. Glutamine prevents gastric oxidative stress in an animal model of portal hypertension gastropathy.

    Science.gov (United States)

    Marques, Camila; Mauriz, José L; Simonetto, Douglas; Marroni, Claudio A; Tuñon, María J; González-Gallego, Javier; Marrón, Norma P

    2011-01-01

    Portal hypertension (PHI) is a clinical syndrome characterized by increases of the blood flow and/or of the vascular resistance in the portal system. A direct consequence of PHI can appearance different lesions on the gastric mucosa and submucosa, cumulatively termed portal hypertensive gastropathy (PHG). To investigate the effects of glutamine on oxidative stress in an experimental model of PHG induced by partial portal vein ligation (PPVL). Portal pressure, transaminase and alkaline phosphatase activity were quantified. Gastric tissue damage was assessed by histological analysis. Oxidative stress was measured by quantification of cytosolic concentration of thiobarbituric acid reactive substances (TBARS), hydroperoxide-initiated chemiluminescence (QL), and nitric oxide (NO) production. Moreover, activities of the antioxidant enzymes superoxide dismutase (SOD), glutathione peroxidase (GPx), and catalase (CAT) were analyzed. Transaminase and alkaline phosphatase activities were not significantly modified by PPVL, indicating absence of liver injury. Histological analysis of gastric sections showed a lost of normal architecture, with edema and vasodilatation. TBARS, QL, and NO production were significantly increased in PPVL animals. A reduction of SOD activity was found. Glutamine administration markedly alleviated histological abnormalities and oxidative stress, normalized SOD activity, and blocked NO overproduction. Our results confirm that the use of molecules with antioxidant capacity can provide protection of the gastric tissue in portal hypertension. Glutamine treatment can be useful to reduce the oxidative damage induced by PHI on gastric tissue.

  4. Comparative kinetic and energetic modelling of phyllosemiquinone oxidation in Photosystem I.

    Science.gov (United States)

    Santabarbara, Stefano; Zucchelli, Giuseppe

    2016-04-14

    The oxidation kinetics of phyllo(semi)quinone (PhQ), which acts as an electron transfer (ET) intermediate in the Photosystem I reaction centre, are described by a minimum of two exponential phases, characterised by lifetimes in the 10-30 ns and 150-300 ns ranges. The fastest phase is considered to be dominated by the oxidation of the PhQ molecule coordinated by the PsaB reaction centre subunit (PhQB), and the slowest phase is dominated by the oxidation of the PsaA coordinated PhQ (PhQA). Testing different energetic schemes within a unified theory-based kinetic modelling approach provides reliable limit-values for some of the physical-chemical parameters controlling these ET reactions: (i) the value of ΔG(0) associated with PhQA oxidation is smaller than ∼+30 meV; (ii) the value of the total reorganisation energy (λt) likely exceeds 0.7 eV; (iii) different mean nuclear modes are coupled to PhQB and PhQA oxidation, the former being larger, and both being ≥100 cm(-1).

  5. Rhesus monkey lens as an in vitro model for studying oxidative stress

    International Nuclear Information System (INIS)

    Zigler, J.S. Jr.; Lucas, V.A.; Du, X.Y.

    1989-01-01

    Lenses from young rhesus monkeys were incubated in the presence of H 2 O 2 or oxygen radical generating systems to determine their suitability as a model for investigating lenticular oxidative stress. Additionally, direct comparisons were made between the effects found with the monkey lenses and those observed with cultured rat lenses exposed to the same oxidizing systems. As in earlier studies with rat lenses the monkey lenses exhibited impaired ability to actively accumulate from the medium radioactively labelled rubidium and choline following exposure to oxidative stress. Based on the effects of various scavengers of oxygen radicals it appeared that the mechanisms responsible for lens damage were the same for both rat and monkey lenses. However, rat lenses were damaged by lower concentrations of oxidants than were monkey lenses. It was concluded that oxidative stress affects both rat and monkey lenses by similar mechanisms but that lenses from monkeys, and probably other primates, are more resistant to these effects because they have better endogenous antioxidant defenses

  6. Mathematical model of the oxidation of ferrous iron by a biofilm of Thiobacillus ferrooxidans.

    Science.gov (United States)

    Mesa, M M; Macías, M; Cantero, D

    2002-01-01

    Microbial oxidation of ferrous iron may be a viable alternative method of producing ferric sulfate, which is a reagent used for removal of H(2)S from biogas. The paper introduces a kinetic study of the biological oxidation of ferrous iron by Thiobacillus ferrooxidans immobilized on biomass support particles (BSP) composed of polyurethane foam. On the basis of the data obtained, a mathematical model for the bioreactor was subsequently developed. In the model described here, the microorganisms adhere by reversible physical adsorption to the ferric precipitates that are formed on the BSP. The model can also be considered as an expression for the erosion of microorganisms immobilized due to the agitation of the medium by aeration.

  7. Shelf-life modeling of bakery products by using oxidation indices.

    Science.gov (United States)

    Calligaris, Sonia; Manzocco, Lara; Kravina, Giuditta; Nicoli, Maria Cristina

    2007-03-07

    The aim of this work was to develop a shelf-life prediction model of lipid-containing bakery products. To this purpose (i) the temperature dependence of the oxidation rate of bakery products was modeled, taking into account the changes in lipid physical state; (ii) the acceptance limits were assessed by sensory analysis; and (iii) the relationship between chemical oxidation index and acceptance limit was evaluated. Results highlight that the peroxide number, the changes of which are linearly related to consumer acceptability, is a representative index of the quality depletion of biscuits during their shelf life. In addition, the evolution of peroxides can be predicted by a modified Arrhenius equation accounting for the changes in the physical state of biscuit fat. Knowledge of the relationship between peroxides and sensory acceptability together with the temperature dependence of peroxide formation allows a mathematical model to be set up to simply and quickly calculate the shelf life of biscuits.

  8. A grey box model of glucose fermentation and syntrophic oxidation in microbial fuel cells.

    Science.gov (United States)

    de Los Ángeles Fernandez, Maria; de Los Ángeles Sanromán, Maria; Marks, Stanislaw; Makinia, Jacek; Gonzalez Del Campo, Araceli; Rodrigo, Manuel; Fernandez, Francisco Jesus

    2016-01-01

    In this work, the fermentative and oxidative processes taking place in a microbial fuel cell (MFC) fed with glucose were studied and modeled. The model accounting for the bioelectrochemical processes was based on ordinary, Monod-type differential equations. The model parameters were estimated using experimental results obtained from three H-type MFCs operated at open or closed circuits and fed with glucose or ethanol. The experimental results demonstrate that similar fermentation processes were carried out under open and closed circuit operation, with the most important fermentation products being ethanol (with a yield of 1.81molmol(-1) glucose) and lactic acid (with a yield of 1.36molmol(-1) glucose). A peak in the electricity generation was obtained when glucose and fermentation products coexisted in the liquid bulk. However, almost 90% of the electricity produced came from the oxidation of ethanol. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Improved stratospheric atmosphere forecasts in the general circulation model through a methane oxidation parametrization

    Science.gov (United States)

    Wang, S.; Jun, Z.

    2017-12-01

    Climatic characteristics of tropical stratospheric methane have been well researched using various satellite data, and numerical simulations have furtherly conducted using chemical climatic models, while the impact of stratospheric methane oxidation on distribution of water vapor is not paid enough attention in general circulation models. Simulated values of water vapour in the tropical upper stratosphere, and throughout much of the extratropical stratosphere, were too low. Something must be done to remedy this deficiency in order to producing realistic stratospheric water vapor using a general circulation model including the whole stratosphere. Introduction of a simple parametrization of the upper-stratospheric moisture source due to methane oxidation and a sink due to photolysis in the mesosphere was conducted. Numerical simulations and analysis of the influence of stratospheric methane on the prediction of tropical stratospheric moisture and temperature fields were carried out. This study presents the advantages of methane oxidation parametrization in producing a realistic distribution of water vapour in the tropical stratosphere and analyzes the impact of methane chemical process on the general circulation model using two storm cases including a heavy rain in South China and a typhoon caused tropical storm.It is obvious that general circulation model with methane oxidation parametrization succeeds in simulating the water vapor and temperature in stratosphere. The simulating rain center value of contrast experiment is increased up to 10% than that of the control experiment. Introduction of methane oxidation parametrization has modified the distribution of water vapour and then producing a broadly realistic distribution of temperature. Objective weather forecast verifications have been performed using simulating results of one month, which demonstrate somewhat positive effects on the model skill. There is a certain extent impact of methane oxidation

  10. A Classical Potential to Model the Adsorption of Biological Molecules on Oxidized Titanium Surfaces.

    Science.gov (United States)

    Schneider, Julian; Ciacchi, Lucio Colombi

    2011-02-08

    The behavior of titanium implants in physiological environments is governed by the thin oxide layer that forms spontaneously on the metal surface and mediates the interactions with adsorbate molecules. In order to study the adsorption of biomolecules on titanium in a realistic fashion, we first build up a model of an oxidized Ti surface in contact with liquid water by means of extensive first-principles molecular dynamics simulations. Taking the obtained structure as reference, we then develop a classical potential to model the Ti/TiOx/water interface. This is based on the mapping with Coulomb and Lennard-Jones potentials of the adsorption energy landscape of single water and ammonia molecules on the rutile TiO2(110) surface. The interactions with arbitrary organic molecules are obtained via standard combination rules to established biomolecular force fields. The transferability of our potential to the case of organic molecules adsorbing on the oxidized Ti surface is checked by comparing the classical potential energy surfaces of representative systems to quantum mechanical results at the level of density functional theory. Moreover, we calculate the heat of immersion of the TiO2 rutile surface and the detachment force of a single tyrosine residue from steered molecular dynamics simulations, finding good agreement with experimental reference data in both cases. As a first application, we study the adsorption behavior of the Arg-Gly-Asp (RGD) peptide on the oxidized titanium surface, focusing particularly on the calculation of the free energy of desorption.

  11. Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

    Science.gov (United States)

    Hanson, Susan K; Baker, R Tom

    2015-07-21

    This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist

  12. Oxidation of elemental mercury in the atmosphere; Constraints imposed by global scale modelling

    Energy Technology Data Exchange (ETDEWEB)

    Bergan, Torbjoern; Rodhe, Henning [Stockholm Univ. (Sweden). Dept. of Meteorology

    2000-05-01

    Based on the global mercury model published by Bergan et al. (1999), we present here further results from simulations where the central theme has been to evaluate the role of ozone and the hydroxyl radical as possible gas phase oxidants for the oxidation of elemental mercury in the atmosphere. The magnitude of natural and man-made mercury emissions are taken from recent literature estimates and the flux from land areas is assumed to vary by season. We consider only two mercury reservoirs, elemental mercury, Hg{sup 0}, and the more soluble divalent form, Hgll. Wet and dry deposition of Hgll is explicitly treated. Applying monthly mean fields of ozone for the oxidation of gas phase Hg{sup 0} and using the reaction rate by Hall (1995) yields a global transformation of Hg{sup 0} to Hgll which is too slow to keep the simulated concentration of Hg{sup 0} near observed values. This shows that there are additional important removal processes for Hg{sup 0} or that the reaction rate proposed by Hall (1995) is too slow. A simulation in which the oxidation rate was artificially increased, so that the global turn-over time of Hg{sup 0} was one year and the simulated average concentration of Hg{sup 0} was realistic, produced latitudinal and seasonal variations in Hg{sup 0} that did not support the hypothesis that gas phase reaction with O{sub 3} is the major oxidation process for Hg{sup 0}. Recent studies indicate that OH may be an important gas phase oxidant for Hg{sup 0}. Using OH as the oxidant and applying the preliminary oxidation rate by Sommar et al. (1999) gave an unrealistically large removal of Hg{sup 0} from the atmosphere. From calculations using a slower reaction rate, corresponding to a turn-over time of Hg{sup 0} of one year, we calculated concentrations of both Hg{sup 0} in surface air and Hgll in precipitation which correspond, both in magnitude and temporal variation, to seasonal observations in Europe and North America. This result supports the suggestion that

  13. Kinetic modeling of low density lipoprotein oxidation in arterial wall and its application in atherosclerotic lesions prediction.

    Science.gov (United States)

    Karimi, Safoora; Dadvar, Mitra; Modarress, Hamid; Dabir, Bahram

    2013-01-01

    Oxidation of low-density lipoprotein (LDL) is one of the major factors in atherogenic process. Trapped oxidized LDL (Ox-LDL) in the subendothelial matrix is taken up by macrophage and leads to foam cell generation creating the first step in atherosclerosis development. Many researchers have studied LDL oxidation using in vitro cell-induced LDL oxidation model. The present study provides a kinetic model for LDL oxidation in intima layer that can be used in modeling of atherosclerotic lesions development. This is accomplished by considering lipid peroxidation kinetic in LDL through a system of elementary reactions. In comparison, characteristics of our proposed kinetic model are consistent with the results of previous experimental models from other researches. Furthermore, our proposed LDL oxidation model is added to the mass transfer equation in order to predict the LDL concentration distribution in intima layer which is usually difficult to measure experimentally. According to the results, LDL oxidation kinetic constant is an important parameter that affects LDL concentration in intima layer so that existence of antioxidants that is responsible for the reduction of initiating rates and prevention of radical formations, have increased the concentration of LDL in intima by reducing the LDL oxidation rate. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  14. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    Amir-Rusli

    1996-01-01

    Analysis modelling of the iron oxide bromination had been carried out using experiment data from the iron oxide bromination in the UT-3 thermochemical cycle. Iron oxide in the form of pellets were made of the calcination of the mixture of iron oxide, silica, graphite and cellulose at 1473 K. Thermobalance reactor was used to study the kinetic reactions of the iron oxide bromination at a temperature of 473 K for 2 - 6 hours. The data collected from the experiments were used as input for the common models. However, none of these models could not explain the result of the experiments. A new model, a combination of two kinetic reactions : exposed particle and coated particle was created and worked successfully

  15. Modeling of simultaneous anaerobic methane and ammonium oxidation in a membrane biofilm reactor.

    Science.gov (United States)

    Chen, Xueming; Guo, Jianhua; Shi, Ying; Hu, Shihu; Yuan, Zhiguo; Ni, Bing-Jie

    2014-08-19

    Nitrogen removal by using the synergy of denitrifying anaerobic methane oxidation (DAMO) and anaerobic ammonium oxidation (Anammox) microorganisms in a membrane biofilm reactor (MBfR) has previously been demonstrated experimentally. In this work, a mathematical model is developed to describe the simultaneous anaerobic methane and ammonium oxidation by DAMO and Anammox microorganisms in an MBfR for the first time. In this model, DAMO archaea convert nitrate, both externally fed and/or produced by Anammox, to nitrite, with methane as the electron donor. Anammox and DAMO bacteria jointly remove the nitrite fed/produced, with ammonium and methane as the electron donor, respectively. The model is successfully calibrated and validated using the long-term (over 400 days) dynamic experimental data from the MBfR, as well as two independent batch tests at different operational stages of the MBfR. The model satisfactorily describes the methane oxidation and nitrogen conversion data from the system. Modeling results show the concentration gradients of methane and nitrogen would cause stratification of the biofilm, where Anammox bacteria mainly grow in the biofilm layer close to the bulk liquid and DAMO organisms attach close to the membrane surface. The low surface methane loadings result in a low fraction of DAMO microorganisms, but the high surface methane loadings would lead to overgrowth of DAMO bacteria, which would compete with Anammox for nitrite and decrease the fraction of Anammox bacteria. The results suggest an optimal methane supply under the given condition should be applied not only to benefit the nitrogen removal but also to avoid potential methane emissions.

  16. Dynamic modelling of nitrous oxide emissions from three Swedish sludge liquor treatment systems

    DEFF Research Database (Denmark)

    Lindblom, E.; Arnell, M.; Flores-Alsina, X.

    2014-01-01

    The objective of this paper is to model the dynamics and validate the results of nitrous oxide (N2O)emissions from three Swedish nitrifying/denitrifying, nitritation and anammox systems treating real anaerobic digester sludge liquor. The Activated Sludge Model No. 1 is extended to describe N2O...... production by both heterotrophic and autotrophic denitrification. In addition, mass transfer equations are implemented to characterize the dynamics of N2O in the water and the gas phases.The biochemical model is simulated and validated for two hydraulic patterns: (1) a sequencing batch reactor; and, (2...

  17. Model-fitting approach to kinetic analysis of non-isothermal oxidation of molybdenite

    International Nuclear Information System (INIS)

    Ebrahimi Kahrizsangi, R.; Abbasi, M. H.; Saidi, A.

    2007-01-01

    The kinetics of molybdenite oxidation was studied by non-isothermal TGA-DTA with heating rate 5 d eg C .min -1 . The model-fitting kinetic approach applied to TGA data. The Coats-Redfern method used of model fitting. The popular model-fitting gives excellent fit non-isothermal data in chemically controlled regime. The apparent activation energy was determined to be about 34.2 kcalmol -1 With pre-exponential factor about 10 8 sec -1 for extent of reaction less than 0.5

  18. Comparison of different two-pathway models for describing the combined effect of DO and nitrite on the nitrous oxide production by ammonia-oxidizing bacteria.

    Science.gov (United States)

    Lang, Longqi; Pocquet, Mathieu; Ni, Bing-Jie; Yuan, Zhiguo; Spérandio, Mathieu

    2017-02-01

    The aim of this work is to compare the capability of two recently proposed two-pathway models for predicting nitrous oxide (N 2 O) production by ammonia-oxidizing bacteria (AOB) for varying ranges of dissolved oxygen (DO) and nitrite. The first model includes the electron carriers whereas the second model is based on direct coupling of electron donors and acceptors. Simulations are confronted to extensive sets of experiments (43 batches) from different studies with three different microbial systems. Despite their different mathematical structures, both models could well and similarly describe the combined effect of DO and nitrite on N 2 O production rate and emission factor. The model-predicted contributions for nitrifier denitrification pathway and hydroxylamine pathway also matched well with the available isotopic measurements. Based on sensitivity analysis, calibration procedures are described and discussed for facilitating the future use of those models.

  19. Short-stack modeling of degradation in solid oxide fuel cells. Part I. Contact degradation

    Energy Technology Data Exchange (ETDEWEB)

    Gazzarri, J.I. [Department of Mechanical Engineering, University of British Columbia, 2054-6250 Applied Science Lane, Vancouver, BC V6T 1Z4 (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, ON M5S 3G8 (Canada)

    2008-01-21

    As the first part of a two paper series, we present a two-dimensional impedance model of a working solid oxide fuel cell (SOFC) to study the effect of contact degradation on the impedance spectrum for the purpose of non-invasive diagnosis. The two dimensional modeled geometry includes the ribbed interconnect, and is adequate to represent co- and counter-flow configurations. Simulated degradation modes include: cathode delamination, interconnect oxidation, and interconnect-cathode detachment. The simulations show differences in the way each degradation mode impacts the impedance spectrum shape, suggesting that identification is possible. In Part II, we present a sensitivity analysis of the results to input parameter variability that reveals strengths and limitations of the method, as well as describing possible interactions between input parameters and concurrent degradation modes. (author)

  20. Short-stack modeling of degradation in solid oxide fuel cells. Part I. Contact degradation

    Science.gov (United States)

    Gazzarri, J. I.; Kesler, O.

    As the first part of a two paper series, we present a two-dimensional impedance model of a working solid oxide fuel cell (SOFC) to study the effect of contact degradation on the impedance spectrum for the purpose of non-invasive diagnosis. The two dimensional modeled geometry includes the ribbed interconnect, and is adequate to represent co- and counter-flow configurations. Simulated degradation modes include: cathode delamination, interconnect oxidation, and interconnect-cathode detachment. The simulations show differences in the way each degradation mode impacts the impedance spectrum shape, suggesting that identification is possible. In Part II, we present a sensitivity analysis of the results to input parameter variability that reveals strengths and limitations of the method, as well as describing possible interactions between input parameters and concurrent degradation modes.

  1. Equilibrium arsenic adsorption onto metallic oxides : Isotherm models, error analysis and removal mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Simsek, Esra Bilgin [Yalova University, Yalova (Turkmenistan); Beker, Ulker [Yldz Technical University, Istanbul (Turkmenistan)

    2014-11-15

    Arsenic adsorption properties of mono- (Fe or Al) and binary (Fe-Al) metal oxides supported on natural zeolite were investigated at three levels of temperature (298, 318 and 338 K). All data obtained from equilibrium experiments were analyzed by Freundlich, Langmuir, Dubinin-Radushkevich, Sips, Toth and Redlich-Peterson isotherms, and error functions were used to predict the best fitting model. The error analysis demonstrated that the As(Ⅴ) adsorption processes were best described by the Dubinin-Raduskevich model with the lowest sum of normalized error values. According to results, the presence of iron and aluminum oxides in the zeolite network improved the As(Ⅴ) adsorption capacity of the raw zeolite (ZNa). The X-ray photoelectron spectroscopy (XPS) analyses of ZNa-Fe and ZNa-AlFe samples suggested that the redox reactions are the postulated mechanisms for the adsorption onto them while the adsorption process is followed by surface complexation reactions for ZNa-Al.

  2. The Semireduced Mechanism for Nitric Oxide Reduction by Non-Heme Diiron Complexes: Modeling Flavodiiron Nitric Oxide Reductases.

    Science.gov (United States)

    White, Corey J; Speelman, Amy L; Kupper, Claudia; Demeshko, Serhiy; Meyer, Franc; Shanahan, James P; Alp, E Ercan; Hu, Michael; Zhao, Jiyong; Lehnert, Nicolai

    2018-02-21

    Flavodiiron nitric oxide reductases (FNORs) are a subclass of flavodiiron proteins (FDPs) capable of preferential binding and subsequent reduction of NO to N 2 O. FNORs are found in certain pathogenic bacteria, equipping them with resistance to nitrosative stress, generated as a part of the immune defense in humans, and allowing them to proliferate. Here, we report the spectroscopic characterization and detailed reactivity studies of the diiron dinitrosyl model complex [Fe 2 (BPMP)(OPr)(NO) 2 ](OTf) 2 for the FNOR active site that is capable of reducing NO to N 2 O [Zheng et al., J. Am. Chem. Soc. 2013, 135, 4902-4905]. Using UV-vis spectroscopy, cyclic voltammetry, and spectro-electrochemistry, we show that one reductive equivalent is in fact sufficient for the quantitative generation of N 2 O, following a semireduced reaction mechanism. This reaction is very efficient and produces N 2 O with a first-order rate constant k > 10 2 s -1 . Further isotope labeling studies confirm an intramolecular N-N coupling mechanism, consistent with the rapid time scale of the reduction and a very low barrier for N-N bond formation. Accordingly, the reaction proceeds at -80 °C, allowing for the direct observation of the mixed-valent product of the reaction. At higher temperatures, the initial reaction product is unstable and decays, ultimately generating the diferrous complex [Fe 2 (BPMP)(OPr) 2 ](OTf) and an unidentified ferric product. These results combined offer deep insight into the mechanism of NO reduction by the relevant model complex [Fe 2 (BPMP)(OPr)(NO) 2 ] 2+ and provide direct evidence that the semireduced mechanism would constitute a highly efficient pathway to accomplish NO reduction to N 2 O in FNORs and in synthetic catalysts.

  3. Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

    Science.gov (United States)

    Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

    2013-02-21

    A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

  4. CFD Model Of A Planar Solid Oxide Electrolysis Cell For Hydrogen Production From Nuclear Energy

    International Nuclear Information System (INIS)

    Grant L. Hawkes; James E. O'Brien; Carl M. Stoots; J. Stephen Herring

    2005-01-01

    A three-dimensional computational fluid dynamics (CFD) model has been created to model high temperature steam electrolysis in a planar solid oxide electrolysis cell (SOEC). The model represents a single cell as it would exist in an electrolysis stack. Details of the model geometry are specific to a stack that was fabricated by Ceramatec2, Inc. and tested at the Idaho National Laboratory. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT2. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified for this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, Nernst potential, operating potential, anode-side gas composition, cathode-side gas composition, current density and hydrogen production over a range of stack operating conditions. Mean model results are shown to compare favorably with experimental results obtained from an actual ten-cell stack tested at INL

  5. Prediction of traffic-related nitrogen oxides concentrations using Structural Time-Series models

    Science.gov (United States)

    Lawson, Anneka Ruth; Ghosh, Bidisha; Broderick, Brian

    2011-09-01

    Ambient air quality monitoring, modeling and compliance to the standards set by European Union (EU) directives and World Health Organization (WHO) guidelines are required to ensure the protection of human and environmental health. Congested urban areas are most susceptible to traffic-related air pollution which is the most problematic source of air pollution in Ireland. Long-term continuous real-time monitoring of ambient air quality at such urban centers is essential but often not realistic due to financial and operational constraints. Hence, the development of a resource-conservative ambient air quality monitoring technique is essential to ensure compliance with the threshold values set by the standards. As an intelligent and advanced statistical methodology, a Structural Time Series (STS) based approach has been introduced in this paper to develop a parsimonious and computationally simple air quality model. In STS methodology, the different components of a time-series dataset such as the trend, seasonal, cyclical and calendar variations can be modeled separately. To test the effectiveness of the proposed modeling strategy, average hourly concentrations of nitrogen dioxide and nitrogen oxides from a congested urban arterial in Dublin city center were modeled using STS methodology. The prediction error estimates from the developed air quality model indicate that the STS model can be a useful tool in predicting nitrogen dioxide and nitrogen oxides concentrations in urban areas and will be particularly useful in situations where the information on external variables such as meteorology or traffic volume is not available.

  6. Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

    Science.gov (United States)

    Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

    2009-04-15

    A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

  7. Fe-oxide Nanoparticles: a natural playground for testing the ISP model

    International Nuclear Information System (INIS)

    Allia, P

    2014-01-01

    Magnetic dipolar interaction plays a major role in systems of ferrimagnetic Fe-oxide nanoparticles. Dipolar interaction plays a role over a wide range of temperatures above blocking temperature and results in the onset of the Interacting Superparamagnetic (ISP) regime. In this paper, distinctive aspects and basic issues of the ISP model are discussed by exploiting the experimental data obtained in well-characterized magnetite nanoparticles

  8. Using multiple biomarkers and determinants to obtain a better measurement of oxidative stress: a latent variable structural equation model approach.

    Science.gov (United States)

    Eldridge, Ronald C; Flanders, W Dana; Bostick, Roberd M; Fedirko, Veronika; Gross, Myron; Thyagarajan, Bharat; Goodman, Michael

    2017-09-01

    Since oxidative stress involves a variety of cellular changes, no single biomarker can serve as a complete measure of this complex biological process. The analytic technique of structural equation modeling (SEM) provides a possible solution to this problem by modelling a latent (unobserved) variable constructed from the covariance of multiple biomarkers. Using three pooled datasets, we modelled a latent oxidative stress variable from five biomarkers related to oxidative stress: F 2 -isoprostanes (FIP), fluorescent oxidation products, mitochondrial DNA copy number, γ-tocopherol (Gtoc) and C-reactive protein (CRP, an inflammation marker closely linked to oxidative stress). We validated the latent variable by assessing its relation to pro- and anti-oxidant exposures. FIP, Gtoc and CRP characterized the latent oxidative stress variable. Obesity, smoking, aspirin use and β-carotene were statistically significantly associated with oxidative stress in the theorized directions; the same exposures were weakly and inconsistently associated with the individual biomarkers. Our results suggest that using SEM with latent variables decreases the biomarker-specific variability, and may produce a better measure of oxidative stress than do single variables. This methodology can be applied to similar areas of research in which a single biomarker is not sufficient to fully describe a complex biological phenomenon.

  9. Modeling arsenite oxidation by chemoautotrophic Thiomonas arsenivorans strain b6 in a packed-bed bioreactor

    Energy Technology Data Exchange (ETDEWEB)

    Dastidar, Aniruddha, E-mail: andy.dastidar@ky.gov [USEPA Research Participant, Division of Water, Frankfort, KY 40601 (United States); Wang, Yi-Tin, E-mail: ywang@engr.uky.edu [Department of Civil Engineering, University of Kentucky, Lexington (United States)

    2012-08-15

    Arsenic is a major toxic pollutant of concern for the human health. Biological treatment of arsenic contaminated water is an alternative strategy to the prevalent conventional treatments. The biological treatment involves a pre-oxidation step transforming the most toxic form of arsenic, As (III), to the least toxic form, As (V), respectively. This intermediate process improves the overall efficiency of total arsenic removal from the contaminated water. As (III) oxidation by the chemoautotrophic bacterium Thiomonas arsenivorans strain b6 was investigated in a fixed-film reactor under variable influent As (III) concentrations (500-4000 mg/L) and hydraulic residence times (HRTs) (0.2-1 day) for a duration of 137 days. During the entire operation, seven steady-state conditions were obtained with As (III) oxidation efficiency ranging from 48.2% to 99.3%. The strong resilience of the culture was exhibited by the recovery of the bioreactor from an As (III) overloading of 5300 {+-} 400 mg As (III)/L day operated at a HRT of 0.2 day. An arsenic mass balance revealed that As (III) was mainly oxidized to As (V) with unaccounted arsenic ({<=} 4%) well within the analytical error of measurement. A modified Monod flux expression was used to determine the biokinetic parameters by fitting the model against the observed steady-state flux data obtained from operating the bioreactor under a range of HRTs (0.2-1 day) and a constant influent As (III) concentration of 500 mg/L. Model parameters, k = 0.71 {+-} 0.1 mg As (III)/mg cells h, and K{sub s} = 13.2 {+-} 2.8 mg As (III)/L were obtained using a non-linear estimation routine and employing the Marquardt-Levenberg algorithm. Sensitivity analysis revealed k to be more sensitive to model simulations of As (III) oxidation under steady-state conditions than parameter K{sub s}. -- Highlights: Black-Right-Pointing-Pointer As (III) oxidation. Black-Right-Pointing-Pointer Biokinetic parameters. Black-Right-Pointing-Pointer Model validation

  10. [Study on the oxidative stress in the ovaries of a rat model of polycystic ovary].

    Science.gov (United States)

    Gong, Jin; Wu, Dong-bo; Zhang, Lan-lan; Li, Jia; Zhao, Xing; Zhang, Dan

    2015-03-01

    To establish a pathological animal model of polycystic ovary (PCO) by letrozole in rats. Investigate whether PCO were mediated by the effect of oxidative stress by measuring oxidative stress levels in this cohort of rats with PCO, and proceed a new way of treatment for polycystic ovary syndrom (PCOS). 90 SD female rats aged 6 weeks were randomly divided into two groups, including a control group of 45 rats that received vehicle only [19% aqueous solution of carboxmethlycellulose (CMC), 1 mL/d] once daily orally (p.o.), and an experimental group of 45 rats, which were administered letrozole at concentrations of 1 mg/kg p.o. dissolved in 1% CMC (1 mL/d) once daily. The treatment period was 28 d. During this period, vaginal smears were collected daily for estrus cycle determination and body masses were measured every 7 d. On the day subsequent to the last letrozole dose administration, rats were killed; Uteri and ovaries were then excised and weighed for the calculation of organ indexes. Serum hormone levels, SHBG and histologic changes in the ovaries were examined. Then testosterone free index (FAD) was calculated. Oxidant status was evaluated by determination of ovarian total oxidant status (TOS), malondialdehyde (MDA) concentration and intracellular reactive oxygen species (ROS) level, while antioxidant status was evaluated by determination of total antioxidant status (TAS) and superoxide dismutase (SOD) concentration. Vaginal smear test showed the estrus cycle began to disappear from day 12 to day 15. A statistically significant difference in growth curves, ovarian weights, uterine weights and organ indexes between the groups were also observed. In rats with PCO serum testosterone (T), follicle-stimulating hormone (FSH) concentrations and free androgen index (FADI) were significantly increased compared with the control group (rats without PCO). However, rats with PCO had decreased levels of estrogen (E2), luteinizing hormone (LH), and progesterone (P) compared

  11. Simplified modeling of simultaneous reaction kinetics of carbon oxidation and nitrification in biofilm processes

    Energy Technology Data Exchange (ETDEWEB)

    Tsuneda, S.; Auresenia, J.; Hibiya, K.; Hirata, A. [Waseda University, Department of Chemical Engineering, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555 (Japan)

    2004-06-01

    Batch experiments with varying initial substrate concentrations and biomass volumes were performed in a three-phase fluidized bed biofilm reactor treating simulated domestic wastewater to study the simultaneous carbon oxidation and nitrification in the biofilm process. A simplified mass balance equation for the biofilm was proposed and five different kinetic rate equations were used to match the actual data. The kinetic parameters were obtained by nonlinear regression analysis on a set of two differential equations representing the simultaneous carbon oxidation and nitrification. The competitive inhibition model incorporating the effects of total organic carbon (TOC) concentrations on nitrification rates was the best-suited model based on the average r{sup 2}. In this model, oxygen concentration and its affinity constants were not included. Instead, it was assumed that the rate of carbon oxidation is independent of the NH{sub 4}{sup +}-N, while nitrification is affected by TOC. The number of parameters was successfully minimized without reducing its ability to accurately predict the bulk concentration time course, which would reduce computational complexity and possibly enhance the availability for an actual wastewater treatment process. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

  12. Considerations in modelling the melting of fuel containing fission products and solute oxides

    International Nuclear Information System (INIS)

    Akbari, F.; Welland, M.J.; Lewis, B.J.; Thompson, W.T.

    2005-01-01

    It is well known that the oxidation of a defected fuel element by steam gives rise to an increase in O/U ratio with a consequent lowering of the incipient melting temperature. Concurrently, the hyperstoichiometry reduces the thermal conductivity thereby raising the centerline fuel pellet temperature for a fixed linear power. The development of fission products soluble in the UO 2 phase or, more important, the deliberate introduction of additive oxides in advanced CANDU fuel bundle designs further affects and generally lowers the incipient melting temperature. For these reasons, the modeling of the molten (hyperstoichiometric) UO 2 phase containing several solute oxides (ZrO 2 , Ln 2 O 3 and AnO 2 ) is advancing in the expectation of developing a moving boundary heat and mass transfer model aimed at better defining the limits of safe operating practice as burnup advances. The paper describes how the molten phase stability model is constructed. The redistribution of components across the solid-liquid interface that attends the onset of melting of a non-stoichiometric UO 2 containing several solutes will be discussed. The issues of how to introduce boundary conditions into heat transfer calculations consistent with the requirements of the Phase Rule will be addressed. The Stefan problem of a moving boundary associated with the solid/liquid interface sets this treatment apart from conventional heat and mass transfer problems. (author)

  13. Model-based evaluation of the role of Anammox on nitric oxide and nitrous oxide productions in membrane aerated biofilm reactor

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Smets, Barth F.; Yuan, Zhiguo

    2013-01-01

    A multispecies one-dimensional biofilm model considering nitric oxide (NO) and nitrous oxide (N2O) productions for membrane aerated biofilm reactor (MABR) that remove nitrogen autotrophically through aerobic ammonia oxidation followed by Anammox is used to study the role of Anammox activity...... on the total nitrogen (TN) removal and the productions of NO and N2O. The model is applied to evaluate how periodic aeration as a control parameter reduces NO and N2O production but maintains high TN removal in MABR. The simulation results show over 3.5% of the removed TN could be attributed to NO and N2O...... production in MABR under the operational conditions optimal for TN removal (72%). An analysis of factors governing the Anammox activity in MABR shows that enhancing Anammox activity not only helps to achieve a high level of nitrogen removal but also reduces NO and N2O productions. Comparison of aeration...

  14. Establishment and calibration of consensus process model for nitrous oxide dynamics in water quality engineering

    DEFF Research Database (Denmark)

    Domingo-Felez, Carlos

    that enhance cost and energy efficiency in BNR, while maintaining effluent quali-ty. Now, increasing attention is placed on direct emissions of nitrous oxide (N2O) as by-product of BNR; N2O is a greenhouse gas (GHG) with a high warming potential and also an ozone depleting chemical compound. Several N2O...... process modelling efforts aim to reproduce ex-perimental data with mathematical equations, structuring our understanding of the system. Various mechanistic models with different structures describ-ing N2O production have been proposed, but no consensus exists between researchers. Hence, the existing plant......-wide GHG models still lack a complete biological process model that can be integrated in a methodology that assess-es N2O emissions and their impact on overall plant performance. A mathematical model structure that describes N2O production during biological nitrogen removal is proposed. Two autotrophic...

  15. Radiolysis study of the oxidation of a vitamin K model compound in ethanolic solution

    International Nuclear Information System (INIS)

    Fackir, L.; Jore, D.; Gardes-Albert, M.; Ferradini, C.; Acher, F.; Azerad, R.

    1993-01-01

    It seems that the biological action of vitamin K (with its important role in carboxylating processes) may involve monoelectronic exchanges. Therefore radical mechanisms of a vitamin K model molecule KHp have been studied in ethanolic solution by mean of steady state radiolysis method. The oxidation of KHp by H 3 C-CH(OH)OO . model peroxyl radicals leads to the formation of a 'dimeric' form of vitamin K. The superoxide anions seem not to be reactive towards KHp in the chosen irradiation conditions

  16. Modelling the growth process of porous aluminum oxide film during anodization

    International Nuclear Information System (INIS)

    Aryslanova, E M; Alfimov, A V; Chivilikhin, S A

    2015-01-01

    Currently it has become important for the development of metamaterials and nanotechnology to obtain regular self-assembled structures. One such structure is porous anodic alumina film that consists of hexagonally packed cylindrical pores. In this work we consider the anodization process, our model takes into account the influence of layers of aluminum and electrolyte on the rate of growth of aluminum oxide, as well as the effect of surface diffusion. In present work we consider those effects. And as a result of our model we obtain the minimum distance between centers of alumina pores in the beginning of anodizing process. (paper)

  17. Modelling the growth process of porous aluminum oxide film during anodization

    Science.gov (United States)

    Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

    2015-11-01

    Currently it has become important for the development of metamaterials and nanotechnology to obtain regular self-assembled structures. One such structure is porous anodic alumina film that consists of hexagonally packed cylindrical pores. In this work we consider the anodization process, our model takes into account the influence of layers of aluminum and electrolyte on the rate of growth of aluminum oxide, as well as the effect of surface diffusion. In present work we consider those effects. And as a result of our model we obtain the minimum distance between centers of alumina pores in the beginning of anodizing process.

  18. Bartter/Gitelman syndromes as a model to study systemic oxidative stress in humans.

    Science.gov (United States)

    Maiolino, Giuseppe; Azzolini, Matteo; Rossi, Gian Paolo; Davis, Paul A; Calò, Lorenzo A

    2015-11-01

    Reactive oxygen species (ROS) are intermediates in reduction-oxidation reactions that begin with the addition of one electron to molecular oxygen, generating the primary ROS superoxide, which in turn interacts with other molecules to produce secondary ROS, such as hydrogen peroxide, hydroxyl radical, and peroxynitrite. ROS are continuously produced during metabolic processes and are deemed to play an important role in cardiovascular diseases, namely, myocardial hypertrophy and fibrosis and atherosclerosis, via oxidative damage of lipids, proteins, and deoxyribonucleic acid. Angiotensin II (Ang II) is a potent vasoactive agent that also exerts mitogenic, proinflammatory, and profibrotic effects through several signaling pathways, in part involving ROS, particularly superoxide and hydrogen peroxide. Moreover, Ang II stimulates NADPH oxidases, leading to higher ROS generation and oxidative stress. Bartter/Gitelman syndrome patients, despite elevated plasma renin activity, Ang II, and aldosterone levels, exhibit reduced peripheral resistance, normal/low blood pressure, and blunted pressor effect of vasoconstrictors. In addition, notwithstanding the activation of the renin-angiotensin system and the increased plasma levels of Ang II, these patients display decreased production of ROS, reduced oxidative stress, and increased antioxidant defenses. In fact, Bartter/Gitelman syndrome patients are characterized by reduced levels of p22(phox) gene expression and undetectable plasma peroxynitrite levels, while showing increased plasma antioxidant power and expression of antioxidant enzymes, such as heme oxygenase-1. In conclusion, multifarious data suggest that Bartter and Gitelman syndrome patients are a model of low oxidative stress and high antioxidant defenses. The contribution offered by the study of these syndromes in elucidating the molecular mechanisms underlying this favorable status could offer chances for new therapeutic targets in disease characterized by high

  19. Experimental and modelling studies of iodine oxide formation and aerosol behaviour relevant to nuclear reactor accidents

    International Nuclear Information System (INIS)

    Dickinson, S.; Auvinen, A.; Ammar, Y.; Bosland, L.; Clément, B.; Funke, F.; Glowa, G.; Kärkelä, T.; Powers, D.A.; Tietze, S.; Weber, G.; Zhang, S.

    2014-01-01

    Highlights: • Radiolytic reactions can influence iodine volatility following a nuclear accident. • Kinetic models have been developed based on atmospheric chemistry studies. • Properties of iodine oxide aerosols produced by radiation have been measured. • Decomposition of iodine oxides by the action of heat or radiation has been observed. - Abstract: Plant assessments have shown that iodine contributes significantly to the source term for a range of accident scenarios. Iodine has a complex chemistry that determines its chemical form and, consequently, its volatility in the containment. If volatile iodine species are formed by reactions in the containment, they will be subject to radiolytic reactions in the atmosphere, resulting in the conversion of the gaseous species into involatile iodine oxides, which may deposit on surfaces or re-dissolve in water pools. The concentration of airborne iodine in the containment will, therefore, be determined by the balance between the reactions contributing to the formation and destruction of volatile species, as well as by the physico-chemical properties of the iodine oxide aerosols which will influence their longevity in the atmosphere. This paper summarises the work that has been done in the framework of the EC SARNET (Severe Accident Research Network) to develop a greater understanding of the reactions of gaseous iodine species in irradiated air/steam atmospheres, and the nature and behaviour of the reaction products. This work has mainly been focussed on investigating the nature and behaviour of iodine oxide aerosols, but earlier work by members of the SARNET group on gaseous reaction rates is also discussed to place the more recent work into context

  20. Mathematical Modeling of Nitrous Oxide Production during Denitrifying Phosphorus Removal Process.

    Science.gov (United States)

    Liu, Yiwen; Peng, Lai; Chen, Xueming; Ni, Bing-Jie

    2015-07-21

    A denitrifying phosphorus removal process undergoes frequent alternating anaerobic/anoxic conditions to achieve phosphate release and uptake, during which microbial internal storage polymers (e.g., Polyhydroxyalkanoate (PHA)) could be produced and consumed dynamically. The PHA turnovers play important roles in nitrous oxide (N2O) accumulation during the denitrifying phosphorus removal process. In this work, a mathematical model is developed to describe N2O dynamics and the key role of PHA consumption on N2O accumulation during the denitrifying phosphorus removal process for the first time. In this model, the four-step anoxic storage of polyphosphate and four-step anoxic growth on PHA using nitrate, nitrite, nitric oxide (NO), and N2O consecutively by denitrifying polyphosphate accumulating organisms (DPAOs) are taken into account for describing all potential N2O accumulation steps in the denitrifying phosphorus removal process. The developed model is successfully applied to reproduce experimental data on N2O production obtained from four independent denitrifying phosphorus removal study reports with different experimental conditions. The model satisfactorily describes the N2O accumulation, nitrogen reduction, phosphate release and uptake, and PHA dynamics for all systems, suggesting the validity and applicability of the model. The results indicated a substantial role of PHA consumption in N2O accumulation due to the relatively low N2O reduction rate by using PHA during denitrifying phosphorus removal.

  1. Thermodynamic and kinetic modelling of fuel oxidation behaviour in operating defective fuel

    International Nuclear Information System (INIS)

    Lewis, B.J.; Thompson, W.T.; Akbari, F.; Thompson, D.M.; Thurgood, C.; Higgs, J.

    2004-01-01

    A theoretical treatment has been developed to predict the fuel oxidation behaviour in operating defective nuclear fuel elements. The equilibrium stoichiometry deviation in the hyper-stoichiometric fuel has been derived from thermodynamic considerations using a self-consistent set of thermodynamic properties for the U-O system, which emphasizes replication of solubilities and three-phase invariant conditions displayed in the U-O binary phase diagram. The kinetics model accounts for multi-phase transport including interstitial oxygen diffusion in the solid and gas-phase transport of hydrogen and steam in the fuel cracks. The fuel oxidation model is further coupled to a heat conduction model to account for the feedback effect of a reduced thermal conductivity in the hyper-stoichiometric fuel. A numerical solution has been developed using a finite-element technique with the FEMLAB software package. The model has been compared to available data from several in-reactor X-2 loop experiments with defective fuel conducted at the Chalk River Laboratories. The model has also been benchmarked against an O/U profile measurement for a spent defective fuel element discharged from a commercial reactor

  2. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    Science.gov (United States)

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

  3. Infertility and recurrent miscarriage with complex II deficiency-dependent mitochondrial oxidative stress in animal models.

    Science.gov (United States)

    Ishii, Takamasa; Yasuda, Kayo; Miyazawa, Masaki; Mitsushita, Junji; Johnson, Thomas E; Hartman, Phil S; Ishii, Naoaki

    2016-04-01

    Oxidative stress is associated with some forms of both male and female infertility. However, there is insufficient knowledge of the influence of oxidative stress on the maintenance of a viable pregnancy, including pregnancy complications and fetal development. There are a number of animal models for understanding age-dependent decrease of reproductive ability and diabetic embryopathy, especially abnormal spermatogenesis, oogenesis and embryogenesis with mitochondrial dysfunctions. Several important processes occur in mitochondria, including ATP synthesis, calcium ion storage, induction of apoptosis and production of reactive oxygen species (ROS). These events have different effects on the several aspects of reproductive function. Tet-mev-1 conditional transgenic mice, developed after studies with the mev-1 mutant of the nematode C. elegans, offer the ability to carefully regulate expression of doxycycline-induced mutated SDHC(V69E) levels and hence modulate endogenous oxidative stress. The mev-1 models have served to illuminate the effects of complex II deficiency-dependent mitochondrial ROS production, although interestingly they maintain normal mitochondrial and intracellular ATP levels. In this review, the reproductive dysfunctions are presented focusing on fertility potentials in each gamete, early embryogenesis, maternal conditions with placental function and neonatal development. Copyright © 2016. Published by Elsevier Ireland Ltd.

  4. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  5. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong

    2015-07-01

    Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

  6. Model study of multiphase DMS oxidation with a focus on halogens

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2004-01-01

    Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

  7. A model for the formation of lattice defects at silicon oxide precipitates in silicon

    International Nuclear Information System (INIS)

    Vanhellemont, J.; Gryse, O. de; Clauws, P.

    2003-01-01

    The critical size of silicon oxide precipitates and the formation of lattice defects by the precipitates are discussed. An expression is derived allowing estimation of self-interstitial emission by spherical precipitates as well as strain build-up during precipitate growth. The predictions are compared with published experimental data. A model for stacking fault nucleation at oxide precipitates is developed based on strain and self-interstitial accumulation during the thermal history of the wafer. During a low-temperature treatment high levels of strain develop. During subsequent high-temperature treatment, excess strain energy in the precipitate is released by self-interstitial emission leading to favourable conditions for stacking fault nucleation

  8. Ab-initio modelling of thermodynamics and kinetics of point defects in indium oxide

    International Nuclear Information System (INIS)

    Agoston, Peter; Klein, Andreas; Albe, Karsten; Erhart, Paul

    2008-01-01

    The electrical and optical properties of indium oxide films strongly vary with the processing parameters. Especially the oxygen partial pressure and temperature determine properties like electrical conductivity, composition and transparency. Since this material owes its remarkable properties like the intrinsic n-type conductivity to its defect chemistry, it is important to understand both, the equilibrium defect thermodynamics and kinetics of the intrinsic point defects. In this contribution we present a defect model based on DFT total energy calculations using the GGA+U method. Further, the nudged elastic band method is employed in order to obtain a set of migration barriers for each defect species. Due to the complicated crystal structure of indium oxide a Kinetic Monte-Carlo algorithm was implemented, which allows to determine diffusion coefficients. The bulk tracer diffusion constant is predicted as a function of oxygen partial pressure, Fermi level and temperature for the pure material

  9. Modeling the solar cycle change in nitric oxide in the thermosphere and upper mesosphere

    International Nuclear Information System (INIS)

    Fuller-Rowell, T.J.

    1993-01-01

    Measurements from the Solar Mesosphere Explorer (SME) satellite have shown that low-latitude nitric oxide densities at 110 km decrease by about a factor of 8 from January 1982 to April 1985. This time period corresponds to the descending phase of the last solar cycle where the monthly smoothed sunspot number decreased from more than 150 to less than 25. In addition, nitric oxide was observed to vary by a factor of 2 over a solar rotation, during high solar activity. A one-dimensional, globally averaged model of the thermosphere and upper mesosphere has been used to study the height distribution of nitric oxide (NO) and its response to changes in the solar extreme ultraviolet radiation (EUV) through the solar cycle and over a solar rotation. The primary source of nitric oxide is the reaction of excited atomic nitrogen, N( 2 D), with molecular oxygen. The atomic nitrogen is created by a number of ion-neutral reactions and by direct dissociation of molecular nitrogen by photons and photoelectrons. The occurrence of the peak nitric oxide density at or below 115 km is a direct consequence of ionization and dissociation of molecular nitrogen by photoelectrons, which are produced by the solar flux below 30.0 nm (XUV). Nitric oxide is shown to vary over the solar cycle by a factor of 7 at low latitudes in the lower thermosphere E region, due to the estimated change in the solar EUV flux, in good agreement with the SME satellite observations. The NO density is shown to be strongly dependent on the temperature profile in the lower thermosphere and accounts for the difference between the current model and previous work. Wavelengths less than 1.8 nm have little impact on the NO profile. A factor of 3 change in solar flux below 5.0 nm at high solar activity produced a factor of 2 change in the peak NO density, consistent with SME observations over a solar rotation; this change also lowered the peak to 100 km, consistent with rocket data. 52 refs., 10 figs., 5 tabs

  10. Modeling and experimental validation of CO heterogeneous chemistry and electrochemistry in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Yurkiv, Vitaly

    2010-12-17

    In the present work experimental and numerical modeling studies of the heterogeneously catalyzed and electrochemical oxidation of CO at Nickel/yttria-stabilized zirconia (YSZ) solid oxide fuel cell (SOFC) anode systems were performed to evaluate elementary charge-transfer reaction mechanisms taking place at the three-phase boundary of CO/CO{sub 2} gas-phase, Ni electrode, and YSZ electrolyte. Temperature-programmed desorption and reaction experiments along with density functional theory calculations were performed to determine adsorption/desorption and surface diffusion kinetics as well as thermodynamic data for the CO/CO{sub 2}/Ni and CO/CO{sub 2}/YSZ systems. Based on these data elementary reaction based models with four different charge transfer mechanisms for the electrochemical CO oxidation were developed and applied in numerical simulations of literature experimental electrochemical data such as polarization curves and impedance spectra. Comparison between simulation and experiment demonstrated that only one of the four charge transfer mechanisms can consistently reproduce the electrochemical data over a wide range of operating temperatures and CO/CO{sub 2} gas compositions. (orig.) [German] In der vorliegenden Arbeit wurden experimentelle und numerische Untersuchungen zur heterogen katalysierten und elektrochemischen Oxidation von CO an Anodensystemen (bestehend aus Nickel und yttriumdotiertem Zirkoniumdioxid, YSZ) von Festoxidbrennstoffzellen (engl. Solid Oxide Fuel Cells, SOFCs) ausgefuehrt, um den mikroskopischen Mechanismus der an der CO/CO{sub 2}-Gasphase/Ni-Elektrode/YSZ-Elektrolyt- Dreiphasen-Grenzflaeche ablaufenden Ladungsuebertragungsreaktion aufzuklaeren. Temperaturprogrammierte Desorptionsmessungen (TPD) und Temperaturprogrammierte Reaktionsmessungen (TPR) sowie Dichtefunktionaltheorierechnungen wurden ausgefuehrt, um adsorptions-, desorptions- und reaktionskinetische sowie thermodynamische Daten fuer die CO/CO{sub 2}/Ni- und CO/CO{sub 2}/YSZ

  11. Thinner inhalation effects on oxidative stress and DNA repair in a rat model of abuse.

    Science.gov (United States)

    Martínez-Alfaro, Minerva; Cárabez-Trejo, Alfonso; Gallegos-Corona, Marco-Antonio; Pedraza-Aboytes, Gustavo; Hernández-Chan, Nancy Georgina; Leo-Amador, Guillermo Enrique

    2010-04-01

    Humans can come into contact with thinner by occupational exposure or by intentional inhalation abuse. Numerous studies of workers for genotoxic effects of thinner exposure have yielded conflicting results, perhaps because co-exposure to variable other compounds cannot be avoided in workplace exposure studies. In contrast, there is no data concerning the genotoxic effects of intentional inhalation abuse. The aim of this project was to examine the genotoxic effects of thinner inhalation in an animal model of thinner abuse (rats exposed to 3000 ppm toluene, a high solvent concentration over a very short, 15 min time period, twice a day for 6 weeks). The data presented here provides evidence that thinner inhalation in our experimental conditions is able to induce weight loss, lung abnormalities and oxidative stress. This oxidative stress induces oxidative DNA damage that is not a characteristic feature of genotoxic damage. No significant difference in DNA damage and DNA repair (biomarkers of genotoxicity) in lymphocytes from thinner-treated and control rats was found. Lead treatment was used as a positive control in these assays. Finally, bone marrow was evaluated as a biomarker of cellular alteration associated with thinner inhalation. The observed absence of hemopoietic and genetic toxicity could be explained in part by the absence of benzene, the only carcinogenic component of thinner; however, benzene is no longer a common component of thinner. In conclusion, thinner did not cause genotoxic effects in an experimental model of intentional abuse despite the fact that thinner inhalation induces oxidative stress. (c) 2009 John Wiley & Sons, Ltd.

  12. Global sensitivity analysis of GEOS-Chem modeled ozone and hydrogen oxides during the INTEX campaigns

    Directory of Open Access Journals (Sweden)

    K. E. Christian

    2018-02-01

    Full Text Available Making sense of modeled atmospheric composition requires not only comparison to in situ measurements but also knowing and quantifying the sensitivity of the model to its input factors. Using a global sensitivity method involving the simultaneous perturbation of many chemical transport model input factors, we find the model uncertainty for ozone (O3, hydroxyl radical (OH, and hydroperoxyl radical (HO2 mixing ratios, and apportion this uncertainty to specific model inputs for the DC-8 flight tracks corresponding to the NASA Intercontinental Chemical Transport Experiment (INTEX campaigns of 2004 and 2006. In general, when uncertainties in modeled and measured quantities are accounted for, we find agreement between modeled and measured oxidant mixing ratios with the exception of ozone during the Houston flights of the INTEX-B campaign and HO2 for the flights over the northernmost Pacific Ocean during INTEX-B. For ozone and OH, modeled mixing ratios were most sensitive to a bevy of emissions, notably lightning NOx, various surface NOx sources, and isoprene. HO2 mixing ratios were most sensitive to CO and isoprene emissions as well as the aerosol uptake of HO2. With ozone and OH being generally overpredicted by the model, we find better agreement between modeled and measured vertical profiles when reducing NOx emissions from surface as well as lightning sources.

  13. A detailed approach to model transport, heterogeneous chemistry, and electrochemistry in solid-oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, V.

    2007-07-01

    This dissertation layes out detailed descriptions for heterogeneous chemistry, electrochemistry, and porous media transport models to simulate solid oxide fuel cells (SOFCs). An elementary like heterogeneous reaction mechanism for the steam reforming of CH4 developed in our research group is used throughout this work. Based on assumption of hydrogen oxidation as the only electrochemical reaction and single step electron transfer reaction as rate limiting, a modified Butler-Volmer equation is used to model the electrochemistry. The pertinence of various porous media transport models such as Modified Fick Model (MFM), Dusty Gas Model (DGM), Mean Transport Pore Model, Modified Maxwell Stefan Model, and Generalized Maxwell Stefan Model under reaction conditions are studied. In general MFM and DGM predictions are in good agreement with experimental data. Physically realistic electrochemical model parameters are very important for fuel cell modeling. Button cell simulations are carried out to deduce the electrochemical model parameters, and those parameters are further used in the modeling of planar cells. Button cell simulations are carried out using the commercial CFD code FLUENT coupled with DETCHEM. For all temperature ranges the model works well in predicting the experimental observations in the high current density region. However, the model predicts much higher open circuit potentials than that observed in the experiments, mainly due to the absence of coking model in the elementary heterogeneous mechanism leading to nonequilibrium compositions. Furthermore, the study presented here employs Nernst equation for the calculation of reversible potential which is strictly valid only for electrochemical equilibrium. It is assumed that the electrochemical charge transfer reaction involving H2 is fast enough to be in equilibrium. However, the comparison of model prediction with thermodynamic equilibrium reveals that this assumption is violated under very low current

  14. Fuel/Oxidizer Injector Modeling in Sub- and Super-Critical Regimes for Deep Throttling Cryogenic Engines, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Accurate CFD modeling of fuel/oxidizer injection and combustion is needed to design and analyze liquid rocket engines. Currently, however, there is no mature...

  15. Sensitivity analysis in oxidation ditch modelling: the effect of variations in stoichiometric, kinetic and operating parameters on the performance indices

    NARCIS (Netherlands)

    Abusam, A.A.A.; Keesman, K.J.; Straten, van G.; Spanjers, H.; Meinema, K.

    2001-01-01

    This paper demonstrates the application of the factorial sensitivity analysis methodology in studying the influence of variations in stoichiometric, kinetic and operating parameters on the performance indices of an oxidation ditch simulation model (benchmark). Factorial sensitivity analysis

  16. Optimization of a new flow design for solid oxide cells using computational fluid dynamics modelling

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig

    2016-01-01

    Design of a gas distributor to distribute gas flow into parallel channels for Solid Oxide Cells (SOC) is optimized, with respect to flow distribution, using Computational Fluid Dynamics (CFD) modelling. The CFD model is based on a 3d geometric model and the optimized structural parameters include...... the width of the channels in the gas distributor and the area in front of the parallel channels. The flow of the optimized design is found to have a flow uniformity index value of 0.978. The effects of deviations from the assumptions used in the modelling (isothermal and non-reacting flow) are evaluated...... and it is found that a temperature gradient along the parallel channels does not affect the flow uniformity, whereas a temperature difference between the channels does. The impact of the flow distribution on the maximum obtainable conversion during operation is also investigated and the obtainable overall...

  17. Modelling irradiation by EM waves of multifunctionalized iron oxide nanoparticles and subsequent drug release

    International Nuclear Information System (INIS)

    Wang, Feng; Calvayrac, Florent; Montembault, Véronique; Fontaine, Laurent

    2015-01-01

    Thermal transport in the environment close to the periphery of the nanoparticle, from a few angstroms to less than a nanometer scale, is becoming increasingly important with the advent of several biomedical applications of multifunctional magnetic nanoparticles, including drug delivery, magnetic resonance imaging, and hyperthermia therapy. We present a multiscale and multiphysics model of the irradiation by electromagnetic waves of radiofrequency of iron oxide nanoparticles functionalized by drug-releasing polymers used as new multifunctional therapeutic compounds against tumors. We compute ab initio the thermal conductivity of the polymer chains as a function of the length, model the unfolding of the polymer after heat transfer from the nanoparticle by molecular mechanics, and develop a multiscale thermodynamic and heat transfer model including the surrounding medium (water) in order to model the drug release. (paper)

  18. A novel approach to model the transient behavior of solid-oxide fuel cell stacks

    Science.gov (United States)

    Menon, Vikram; Janardhanan, Vinod M.; Tischer, Steffen; Deutschmann, Olaf

    2012-09-01

    This paper presents a novel approach to model the transient behavior of solid-oxide fuel cell (SOFC) stacks in two and three dimensions. A hierarchical model is developed by decoupling the temperature of the solid phase from the fluid phase. The solution of the temperature field is considered as an elliptic problem, while each channel within the stack is modeled as a marching problem. This paper presents the numerical model and cluster algorithm for coupling between the solid phase and fluid phase. For demonstration purposes, results are presented for a stack operated on pre-reformed hydrocarbon fuel. Transient response to load changes is studied by introducing step changes in cell potential and current. Furthermore, the effect of boundary conditions and stack materials on response time and internal temperature distribution is investigated.

  19. Anti-inflammatory effects and anti-oxidant capacity of Myrathius arboreus (Cecropiaceae) in experimental models.

    Science.gov (United States)

    Oluwole, Oluwafemi Gabriel; Ologe, Olufunmilayo; Alabi, Akinyinka; Tunde Yusuf, Ganiyu; Umukoro, Solomon

    2017-11-27

    Inflammation is involved in various diseases; search for safe treatments is warranted. Anti-inflammatory effects of ethanol extract of Myrathius arboreus (EEMa) were studied in carrageenan-induced model, formaldehyde sub-acute-induced model, and in 48 h lipopolysaccharide-induced air pouch model of inflammation. EEMa membrane-stabilizing activities and anti-oxidant capacity were determined in vitro. In the carrageenan model EEMa (125, 250, or 500 mg/kg), indomethacin (5 mg/kg), or vehicle 3 mL/kg was administered orally in rats (n=5). After 1 h, 0.1 mL of 1% carrageenan was injected into the right hind paw of rats. Change in edema sizes was measured for 3 h with plethysmometer. One-tenth milliliter (0.1 mL) of 2.5% formaldehyde was injected into the rat paw on the first day and the third day to induce sub-acute inflammation; changes in the edema sizes were determined, and percentages of inhibitions were calculated. Anti-inflammatory effects of EEMa were further examined in lipopolysaccharide (LPS)-induced air-pouch based on leukocytes count, volume of exudates, levels of malondialdehyde, glutathione, superoxide dismutase, nitric oxides, and tumor necrosis factor released into the inflammatory fluids. EEMa-free radicals scavenging activities were studied in DPPH and reducing power tests. Membrane-stabilizing activities of EEMa were evaluated in the red blood cell lysis induced by thermal and hypotonic solution. EEMa (250, 500 mg/kg) produced significant (p<0.001; p<0.05) inhibition of inflammation when compared with vehicle. Also, EEMa (250, 500, or 1000 μg/mL) significantly stabilized membrane and produced free radical scavenging activities. M. arboreus possesses anti-inflammatory and the anti-oxidant properties that might benefit translational medicine.

  20. Oral absorption and oxidative metabolism of atrazine in rats evaluated by physiological modeling approaches

    International Nuclear Information System (INIS)

    McMullin, Tami S.; Hanneman, William H.; Cranmer, Brian K.; Tessari, John D.; Andersen, Melvin E.

    2007-01-01

    Atrazine (ATRA) is metabolized by cytochrome P450s to the chlorinated metabolites, 2-chloro-4-ethylamino-6-amino-1,3,5-triazine (ETHYL), 2-chloro-4-amino-6-isopropylamino-1, 3, 5-triazine (ISO), and diaminochlorotriazine (DACT). Here, we develop a set of physiologically based pharmacokinetic (PBPK) models that describe the influence of oral absorption and oxidative metabolism on the blood time course curves of individual chlorotriazines (Cl-TRIs) in rat after oral dosing of ATRA. These models first incorporated in vitro metabolic parameters to describe time course plasma concentrations of DACT, ETHYL, and ISO after dosing with each compound. Parameters from each individual model were linked together into a final composite model in order to describe the time course of all 4 Cl-TRIs after ATRA dosing. Oral administration of ISO, ETHYL and ATRA produced double peaks of the compounds in plasma time courses that were described by multiple absorption phases from gut. An adequate description of the uptake and bioavailability of absorbed ATRA also required inclusion of additional oxidative metabolic clearance of ATRA to the mono-dealkylated metabolites occurring in GI a tract compartment. These complex processes regulating tissue dosimetry of atrazine and its chlorinated metabolites likely reflect limited compound solubility in the gut from dosing with an emulsion, and sequential absorption and metabolism along the GI tract at these high oral doses

  1. Mechanistic modelling of a cathode-supported tubular solid oxide fuel cell

    Science.gov (United States)

    Suwanwarangkul, R.; Croiset, E.; Pritzker, M. D.; Fowler, M. W.; Douglas, P. L.; Entchev, E.

    A two-dimensional mechanistic model of a tubular solid oxide fuel cell (SOFC) considering momentum, energy, mass and charge transport is developed. The model geometry of a single cell comprises an air-preheating tube, air channel, fuel channel, anode, cathode and electrolyte layers. The heat radiation between cell and air-preheating tube is also incorporated into the model. This allows the model to predict heat transfer between the cell and air-preheating tube accurately. The model is validated and shows good agreement with literature data. It is anticipated that this model can be used to help develop efficient fuel cell designs and set operating variables under practical conditions. The transport phenomena inside the cell, including gas flow behaviour, temperature, overpotential, current density and species concentration, are analysed and discussed in detail. Fuel and air velocities are found to vary along flow passages depending on the local temperature and species concentrations. This model demonstrates the importance of incorporating heat radiation into a tubular SOFC model. Furthermore, the model shows that the overall cell performance is limited by O 2 diffusion through the thick porous cathode and points to the development of new cathode materials and designs being important avenues to enhance cell performance.

  2. Air oxidation of Zircaloy-4 in the 600-1000 °C temperature range: Modeling for ASTEC code application

    Science.gov (United States)

    Coindreau, O.; Duriez, C.; Ederli, S.

    2010-10-01

    Progress in the treatment of air oxidation of zirconium in severe accident (SA) codes are required for a reliable analysis of severe accidents involving air ingress. Air oxidation of zirconium can actually lead to accelerated core degradation and increased fission product release, especially for the highly-radiotoxic ruthenium. This paper presents a model to simulate air oxidation kinetics of Zircaloy-4 in the 600-1000 °C temperature range. It is based on available experimental data, including separate-effect experiments performed at IRSN and at Forschungszentrum Karlsruhe. The kinetic transition, named "breakaway", from a diffusion-controlled regime to an accelerated oxidation is taken into account in the modeling via a critical mass gain parameter. The progressive propagation of the locally initiated breakaway is modeled by a linear increase in oxidation rate with time. Finally, when breakaway propagation is completed, the oxidation rate stabilizes and the kinetics is modeled by a linear law. This new modeling is integrated in the severe accident code ASTEC, jointly developed by IRSN and GRS. Model predictions and experimental data from thermogravimetric results show good agreement for different air flow rates and for slow temperature transient conditions.

  3. Mathematical modeling of nitrous oxide (N2O) emissions from full-scale wastewater treatment plants.

    Science.gov (United States)

    Ni, Bing-Jie; Ye, Liu; Law, Yingyu; Byers, Craig; Yuan, Zhiguo

    2013-07-16

    Mathematical modeling of N2O emissions is of great importance toward understanding the whole environmental impact of wastewater treatment systems. However, information on modeling of N2O emissions from full-scale wastewater treatment plants (WWTP) is still sparse. In this work, a mathematical model based on currently known or hypothesized metabolic pathways for N2O productions by heterotrophic denitrifiers and ammonia-oxidizing bacteria (AOB) is developed and calibrated to describe the N2O emissions from full-scale WWTPs. The model described well the dynamic ammonium, nitrite, nitrate, dissolved oxygen (DO) and N2O data collected from both an open oxidation ditch (OD) system with surface aerators and a sequencing batch reactor (SBR) system with bubbling aeration. The obtained kinetic parameters for N2O production are found to be reasonable as the 95% confidence regions of the estimates are all small with mean values approximately at the center. The model is further validated with independent data sets collected from the same two WWTPs. This is the first time that mathematical modeling of N2O emissions is conducted successfully for full-scale WWTPs. While clearly showing that the NH2OH related pathways could well explain N2O production and emission in the two full-scale plants studied, the modeling results do not prove the dominance of the NH2OH pathways in these plants, nor rule out the possibility of AOB denitrification being a potentially dominating pathway in other WWTPs that are designed or operated differently.

  4. Modified Wagner model for the active-to-passive transition in the oxidation of Si3N4

    International Nuclear Information System (INIS)

    Wang Junjie; Zhang Litong; Zeng Qingfeng; Cheng Laifei; Xu Yongdong

    2008-01-01

    Si 3 N 4 is used as the coating material of space shuttle structures which receive very high thermal fluxes during the atmospheric re-entry phase. Two main regimes govern the oxidation of Si 3 N 4 : the passive oxidation, with the formation of a protective silica layer leading generally to a mass gain, and the active oxidation, with vaporization of SiO leading to a mass loss of the sample. To ensure that silicon nitride will efficiently protect a material in given oxidizing environments, its own oxidation behaviour must be previously known. Therefore, the active-to-passive transition of Si 3 N 4 oxidation is a problem of deep scientific importance and of wide technological relevance. In this paper, a modified Wager model for the active-to-passive transition in the oxidation of Si 3 N 4 is presented, which includes the non-equilibrium effects caused by the mass transfer. The present theoretical calculations satisfactorily explained the reported experimental and theoretical data. The influence of flow rate on the active-to-passive transition boundary has been explained using our model. The rate controlling mechanism of the oxidation at the active-to-passive transition point is proposed

  5. Redox proteomic evaluation of oxidative modification and recovery in a 3D reconstituted human skin tissue model exposed to UVB.

    Science.gov (United States)

    Dyer, J M; Haines, S R; Thomas, A; Wang, W; Walls, R J; Clerens, S; Harland, D P

    2017-04-01

    Exposure to UV in humans resulting in sunburn triggers a complex series of events that are a mix of immediate and delayed damage mediation and healing. While studies on the effects of UV exposure on DNA damage and repair have been reported, changes in the oxidative modification of skin proteins are poorly understood at the molecular level, despite the important role played by structural proteins in skin tissue, and the effect of the integrity of these proteins on skin appearance and health. Proteomic molecular mapping of oxidation was here applied to try to enhance understanding of skin damage and recovery from oxidative damage and UVB exposure. A redox proteomic-based approach was applied to evaluating skin protein modification when exposed to varying doses of UVB after initial oxidative stress, via tracking changes in protein oxidation during the healing process in vitro using a full-thickness reconstituted human skin tissue model. Bioassays and structural evaluation confirmed that our cultured skin tissues underwent a normal physiological response to UVB exposure. A set of potential skin marker peptides was generated, for use in tracking skin protein oxidative modification. Exposure to UVB after thermal oxidative stress was found to result in higher levels of skin protein oxidation than a non-irradiated control for up to seven days after exposure. Recovery of the skin proteins from oxidative stress, as assessed by the overall protein oxidation levels, was found to be impaired by UVB exposure. Oxidative modification was largely observed in skin structural proteins. Exposure of skin proteins to UVB exacerbates oxidative damage to structural skin proteins, with higher exposure levels leading to increasingly impaired recovery from this damage. This has potential implications for the functional performance of the proteins and inter-related skin health and cosmetic appearance. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  6. Modeling and Experimental Studies of Mercury Oxidation and Adsorption in a Fixed-Bed Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Buitrago, Paula A.; Morrill, Mike; Lighty, JoAnn S.; Silcox, Geoffrey D.

    2009-06-15

    This report presents experimental and modeling mercury oxidation and adsorption data. Fixed-bed and single-particle models of mercury adsorption were developed. The experimental data were obtained with two reactors: a 300-W, methane-fired, tubular, quartz-lined reactor for studying homogeneous oxidation reactions and a fixed-bed reactor, also of quartz, for studying heterogeneous reactions. The latter was attached to the exit of the former to provide realistic combustion gases. The fixed-bed reactor contained one gram of coconut-shell carbon and remained at a temperature of 150°C. All methane, air, SO2, and halogen species were introduced through the burner to produce a radical pool representative of real combustion systems. A Tekran 2537A Analyzer coupled with a wet conditioning system provided speciated mercury concentrations. At 150°C and in the absence of HCl or HBr, the mercury uptake was about 20%. The addition of 50 ppm HCl caused complete capture of all elemental and oxidized mercury species. In the absence of halogens, SO2 increased the mercury adsorption efficiency to up to 30 percent. The extent of adsorption decreased with increasing SO2 concentration when halogens were present. Increasing the HCl concentration to 100 ppm lessened the effect of SO2. The fixed-bed model incorporates Langmuir adsorption kinetics and was developed to predict adsorption of elemental mercury and the effect of multiple flue gas components. This model neglects intraparticle diffusional resistances and is only applicable to pulverized carbon sorbents. It roughly describes experimental data from the literature. The current version includes the ability to account for competitive adsorption between mercury, SO2, and NO2. The single particle model simulates in-flight sorbent capture of elemental mercury. This model was developed to include Langmuir and Freundlich isotherms, rate equations, sorbent feed rate, and

  7. The effect of consuming oxidized oil supplemented with fiber on lipid profiles in rat model

    Directory of Open Access Journals (Sweden)

    Shila Shafaeizadeh

    2011-01-01

    Conclusions: Pectin consumption could decrease serum malondialdehyde and cholesterol in the diet that contains oxidized oil. Pectin supplementation could decrease the detrimental effects of thermally oxidized oil.

  8. Effects of Laminaria japonica polysaccharides on exercise endurance and oxidative stress in forced swimming mouse model.

    Science.gov (United States)

    Yan, Feiwei; Hao, Haitao

    2016-12-01

    Polysaccharides are the major active ingredients responsible for the bioactivities of Laminaria japonica. However, the effects of L. japonica polysaccharides (LJP) on exercise endurance and oxidative stress have never been investigated. Therefore, this study was conducted to investigate the effects of LJP on exercise endurance and oxidative stress in a forced swimming mouse model. The animals were divided into four groups, namely the control (C), LJP-75, LJP-150, and LJP-300 groups, which received physiological saline and 75, 150, and 300 mg kg(-1) LJP, respectively, by gavage once a day for 28 days. This was followed by a forced swimming test and measurements of various biochemical parameters. LJP increased swimming time to exhaustion, the liver and muscle glycogen content, and levels of superoxide dismutase, glutathione peroxidase, and catalase in the serum, liver, and muscle, which were accompanied by corresponding decreases in the malondialdehyde (MDA) content of the same tissues. Furthermore, decreases in blood lactic acid and serum myeloperoxidase (MPO) levels were observed. LJP enhanced exercise endurance and protected mice against exhaustive exercise-induced oxidative stress.

  9. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lü, Hongying, E-mail: hylv@ytu.edu.cn; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

    2014-08-30

    Highlights: • A protic ionic liquid, [Hnmp]HCOO, was used as in ODS. • The mechanism of ODS was involved in dual activation by the PIL. • The [Hnmp]HCOO exhibited high catalytic activity in ODS. • The amounts of PILs and oxidant dosage play vital roles in desulfurization system. • This system can be recycled five times with an unnoticeable decrease in activity. - Abstract: A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and {sup 1}H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50 °C in 3 h under conditions of V{sub PIL}/V{sub model} {sub oil} = 1:10 and H{sub 2}O{sub 2}/DBT (O/S, molar ratio) = 5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity.

  10. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid

    International Nuclear Information System (INIS)

    Lü, Hongying; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

    2014-01-01

    Highlights: • A protic ionic liquid, [Hnmp]HCOO, was used as in ODS. • The mechanism of ODS was involved in dual activation by the PIL. • The [Hnmp]HCOO exhibited high catalytic activity in ODS. • The amounts of PILs and oxidant dosage play vital roles in desulfurization system. • This system can be recycled five times with an unnoticeable decrease in activity. - Abstract: A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and 1 H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50 °C in 3 h under conditions of V PIL /V model oil = 1:10 and H 2 O 2 /DBT (O/S, molar ratio) = 5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity

  11. Kinetic Modeling of Methionine Oxidation in Monoclonal Antibodies from Hydrogen Peroxide Spiking Studies.

    Science.gov (United States)

    Hui, Ada; Lam, Xanthe M; Kuehl, Christopher; Grauschopf, Ulla; Wang, Y John

    2015-01-01

    When isolator technology is applied to biotechnology drug product fill-finish process, hydrogen peroxide (H2O2) spiking studies for the determination of the sensitivity of protein to residual peroxide in the isolator can be useful for assessing a maximum vapor phase hydrogen peroxide (VPHP) level. When monoclonal antibody (mAb) drug products were spiked with H2O2, an increase in methionine (Met 252 and Met 428) oxidation in the Fc region of the mAbs with a decrease in H2O2 concentration was observed for various levels of spiked-in peroxide. The reaction between Fc-Met and H2O2 was stoichiometric (i.e., 1:1 molar ratio), and the reaction rate was dependent on the concentrations of mAb and H2O2. The consumption of H2O2 by Fc-Met oxidation in the mAb followed pseudo first-order kinetics, and the rate was proportional to mAb concentration. The extent of Met 428 oxidation was half of that of Met 252, supporting that Met 252 is twice as reactive as Met 428. Similar results were observed for free L-methionine when spiked with H2O2. However, mAb formulation excipients may affect the rate of H2O2 consumption. mAb formulations containing trehalose or sucrose had faster H2O2 consumption rates than formulations without the sugars, which could be the result of impurities (e.g., metal ions) present in the excipients that may act as catalysts. Based on the H2O2 spiking study results, we can predict the amount Fc-Met oxidation for a given protein concentration and H2O2 level. Our kinetic modeling of the reaction between Fc-Met oxidation and H2O2 provides an outline to design a H2O2 spiking study to support the use of VPHP isolator for antibody drug product manufacture. Isolator technology is increasing used in drug product manufacturing of biotherapeutics. In order to understand the impact of residual vapor phase hydrogen peroxide (VPHP) levels on protein product quality, hydrogen peroxide (H2O2) spiking studies may be performed to determine the sensitivity of monoclonal antibody

  12. Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

    Science.gov (United States)

    Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

    2017-02-15

    Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. The OH-initiated oxidation of atmospheric peroxyacetic acid: Experimental and model studies

    Science.gov (United States)

    Wu, Huihui; Wang, Yin; Li, Huan; Huang, Liubin; Huang, Dao; Shen, Hengqing; Xing, Yanan; Chen, Zhongming

    2017-09-01

    Peroxyacetic acid (PAA, CH3C(O)OOH) plays an important role in atmospheric chemistry, serving as reactive oxidant and affecting radical recycling. However, previous studies revealed an obvious gap between modelled and observed concentrations of atmospheric PAA, which may be partly ascribed to the uncertainty in the kinetics and mechanism of OH-oxidation. In this study, we measured the rate constant of OH radical reaction with PAA (kPAA+OH) and investigated the products in order to develop a more robust atmospheric PAA chemistry. Using the relative rates technique and employing toluene and meta-xylene as reference compounds, the kPAA+OH was determined to be (9.4-11.9) × 10-12 cm3 molecule-1 s-1 at 298 K and 1 atm, which is about (2.5-3.2) times larger than that parameter used in Master Chemical Mechanism v3.3.1 (MCM v3.3.1) (3.70 × 10-12 cm3 molecule-1 s-1). Incorporation of a box model and MCM v3.3.1 with revised PAA chemistry represented a better simulation of atmospheric PAA observed during Wangdu Campaign 2014, a rural site in North China Plain. It is found that OH-oxidation is an important sink of atmospheric PAA in this rural area, accounting for ∼30% of the total loss. Moreover, the major terminal products of PAA-OH reaction were identified as formaldehyde (HCHO) and formic acid (HC(O)OH). The modelled results show that both primary and secondary chemistry play an important role in the large HCHO and HC(O)OH formation under experimental conditions. There should exist the channel of methyl H-abstraction for PAA-OH reaction, which may also provide routes to HCHO and HC(O)OH formation.

  14. Experimental and Kinetic Modeling Study of Ethyl Levulinate Oxidation in a Jet-Stirred Reactor

    KAUST Repository

    Wang, Jui-Yang

    2017-06-01

    A jet-stirred reactor was designed and constructed in the Clean Combustion Research Center (CCRC) at King Abdullah University of Science and Technology (KAUST); was validated with n-heptane, iso-octane oxidation and cyclohexene pyrolysis. Different configurations of the setup have been tested to achieve good agreement with results from the literature. Test results of the reactor indicated that installation of a pumping system at the downstream side in the experimental apparatus was necessary to avoid the reoccurrence of reactions in the sampling probe. Experiments in ethyl levulinate oxidation were conducted in the reactor under several equivalence ratios, from 600 to 1000 K, 1 bar and 2 s residence time. Oxygenated species detected included methyl vinyl ketone, levulinic acid and ethyl acrylate. Ethylene, methane, carbon monoxide, hydrogen, oxygen and carbon dioxide were further quantified with a gas chromatography, coupled with a flame ionization detector and a thermal conductivity detector. The ethyl levulinate chemical kinetic model was first developed by Dr. Stephen Dooley, Trinity College Dublin, and simulated under the same conditions, using the Perfect-Stirred Reactor code in Chemkin software. In comparing the simulation results with experimental data, some discrepancies were noted; predictions of ethylene production were not well matched. The kinetic model was improved by updating several classes of reactions: unimolecular decomposition, H-abstraction, C-C and C-O beta-scissions of fuel radicals. The updated model was then compared again with experimental results and good agreement was achieved, proving that the concerted eliminated reaction is crucial for the kinetic mechanism formulation of ethyl levulinate. In addition, primary reaction pathways and sensitivity analysis were performed to describe the role of molecular structure in combustion (800 and 1000 K for ethyl levulinate oxidation in the jet-stirred reactor).

  15. An extension of a high temperature creep model to account for fuel sheath oxidation

    International Nuclear Information System (INIS)

    Boccolini, G.; Valli, G.

    1983-01-01

    Starting from the high-temperature creep model for Zircaloy fuel sheathing, the NIRVANA (developed by AECL), a multilayer model, is proposed in this paper: it includes the outer oxide plus alpha retained layers, and the inner core of beta or alpha plus beta material, all constrained to deform with the same creep rate. The model has been incorporated into the SPARA fuel computer code developed for the transient analysis of fuel rod behaviour in the CIRENE prototype reactor, but it is in principle valid for all Zircaloy fuel sheathings. Its predictions are compared with experimental results from burst tests on BWR and PWR type sheaths; the tests were carried out at CNEN under two research contracts with Ansaldo Meccanico Nucleare and Sigen-Sopren, respectively

  16. A model for the Space Shuttle Main Engine High Pressure Oxidizer Turbopump shaft seal system

    Science.gov (United States)

    Paxson, Daniel E.

    1990-01-01

    A model of the High Pressure Oxidizer Turbopump (HPOTP) shaft seal system on the Space Shuttle Main Engine (SSME) is described. The model predicts the fluid properties and flow rates throughout this system for a number of conditions simulating failed seals. The results agree well with qualitative expectations and redline values but cannot be verified with actual data due to the lack thereof. The results indicate that each failure mode results in a unique distribution of properties throughout the seal system and can therefore be individually identified given the proper instrumentation. Furthermore, the detection process can be built on the principle of qualitative reasoning without the use of exact fluid property values. A simplified implementation of the model which does not include the slinger/labyrinth seal combination has been developed and will be useful for inclusion in a real-time diagnostic system.

  17. Modelling of catalytic oxidation of NH3 and reduction of NO on limestone during sulphur capture

    DEFF Research Database (Denmark)

    Kiil, Søren; Bhatia, Suresh K.; Dam-Johansen, Kim

    1996-01-01

    activity with respect to each species involved. An existing particle model, the Grain-Micrograin Model, which simulates sulphur capture on limestone under oxidizing conditions is considered in the modelling. Simulation results in good qualitative agreement with experimental data are obtained here......A theoretical study of the complex transient system of simultaneous sulphur capture and catalytic reactions of N-containing compounds taking place on a single limestone particle is conducted. The numerical technique developed previously by the authors (Kiil et al. 1994) based on collocation...... for the catalytic chemistry of NH3 during simultaneous sulphur capture on a Stevns Chalk particle. The reduction of NO by NH3 over CaSO4 (which is the product of the reaction between SO2, O2 and limestone) was found to be important because this reaction could explain the change in selectivity with increased solid...

  18. Obesity decreases the oxidant stress induced by tobacco smoke in a rat model.

    Science.gov (United States)

    Montaño, Martha; Pérez-Ramos, J; Esquivel, A; Rivera-Rosales, R; González-Avila, G; Becerril, C; Checa, M; Ramos, C

    2016-09-01

    Obesity and emphysema are associated with low-grade systemic inflammation and oxidant stress. Assuming that the oxidant stress induced by emphysema would be decreased by obesity, we analyzed the oxidant/antioxidant state in a rat model combining both diseases simultaneously. Obesity was induced using sucrose, while emphysema by exposure to tobacco smoke. End-points evaluated were: body weight, abdominal fat, plasma dyslipidemia and malondialdehyde (MDA), insulin and glucose AUC, activities of Mn-superoxide dismutase (Mn-SOD), glutathione reductase (GR), glutathione transferase (GST) and glutathione peroxidase (GPx); lung MnSOD and 3-nitrotyrosine (3-NT) immunostaining, and expression of αV and β6 integrin subunits. In rats with obesity, the body weight, abdominal fat, plasma triglyceride levels, glucose AUC, insulin levels, GST activity, and αV and β6 integrin expressions were amplified. The rats with emphysema had lower values of body weight, abdominal fat, plasma insulin, triglycerides and glucose AUC but higher values of plasma MDA, GPx activity, and the lung expression of the αV and β6 integrins. The combination of obesity and emphysema compared to either condition alone led to diminished body weight, abdominal fat, plasma insulin MDA levels, GPx and GST activities, and αV and β6 integrin expressions; these parameters were all previously increased by obesity. Immunostaining for MnSOD augmented in all experimental groups, but the staining for 3-NT only increased in rats treated with tobacco alone or combined with sucrose. Results showed that obesity reduces oxidant stress and integrin expression, increasing antioxidant enzyme activities; these changes seem to partly contribute to a protective mechanism of obesity against emphysema development.

  19. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

  20. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    International Nuclear Information System (INIS)

    Rau, M.S.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2010-01-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H 2 SO 4 solution at different rotation rates (ω). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on ω 1/2 . On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

  1. Role of Renin-Angiotensin System and Oxidative Stress on Vascular Inflammation in Insulin Resistence Model

    OpenAIRE

    Renna, N. F.; Lembo, C.; Diez, E.; Miatello, R. M.

    2013-01-01

    (1) is study aims to demonstrate the causal involvement of renin angiotensin system (RAS) and oxidative stress (OS) on vascular inammation in an experimental model of metabolic syndrome (MS) achieved by fructose administration to spontaneously hypertensive rats (FFHR) during 12 weeks. (2) Chronic treatment with candesartan (C) (10 mg/kg per day for the last 6 weeks) or 4OH-Tempol (T) (10−3 mmol/L in drinking water for the last 6 weeks) reversed the increment in metabolic variables and systo...

  2. Molecular-level chemistry of model single-crystal oxide surfaces with model halogenated compounds

    Science.gov (United States)

    Adib, Kaveh

    Synchrotron-based X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD) and low energy electron diffraction (LEED) have been used to investigate, at a molecular level, the chemistry of different terminations of single crystal iron-oxide surfaces with probe molecules (CCl4 and D2O). Comparisons of the reactivity of these surfaces towards CCl4, indicate that the presence of an uncapped surface Fe cation (strong Lewis acid site) and an adjacent oxygen site capped by that cation can effect the C-Cl bond cleavage in CCl4, resulting in dissociatively adsorbed Cl-adatoms and carbon-containing fragments. If in addition to these sites, an uncapped surface oxygen (Lewis base) site is also available, the carbon-containing moiety can then move that site, coordinate itself with that uncapped oxygen, and stabilize itself. At a later step, the carbon-containing fragment may form a strong covalent bond with the uncapped oxygen and may even abstract that surface oxygen. On the other hand, if an uncapped oxygen is not available to stabilize the carbon-containing fragment, the surface coordination will not occur and upon the subsequent thermal annealing of the surface the Cl-adatoms and the carbon-containing fragments will recombine and desorb as CCl4. Finally, the presence of surface deuteroxyls blocking the strong Lewis acid and base sites of the reactive surface, passivates this surface. Such a deuteroxylated surface will be unreactive towards CCl 4. Such a molecular level understanding of the surface chemistry of metal-oxides will have applications in the areas of selective catalysis, including environmental catalysis, and chemical sensor technology.

  3. Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

    Science.gov (United States)

    Lashina, Elena A; Kaichev, Vasily V; Saraev, Andrey A; Vinokurov, Zakhar S; Chumakova, Nataliya A; Chumakov, Gennadii A; Bukhtiyarov, Valerii I

    2017-09-21

    The self-sustained kinetic oscillations in the oxidation of CH 4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO 2 , H 2 , and H 2 O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.

  4. Neonatal Maturation of Paracetamol (Acetaminophen) Glucuronidation, Sulfation, and Oxidation Based on a Parent-Metabolite Population Pharmacokinetic Model.

    Science.gov (United States)

    Cook, Sarah F; Stockmann, Chris; Samiee-Zafarghandy, Samira; King, Amber D; Deutsch, Nina; Williams, Elaine F; Wilkins, Diana G; Sherwin, Catherine M T; van den Anker, John N

    2016-11-01

    This study aimed to model the population pharmacokinetics of intravenous paracetamol and its major metabolites in neonates and to identify influential patient characteristics, especially those affecting the formation clearance (CL formation ) of oxidative pathway metabolites. Neonates with a clinical indication for intravenous analgesia received five 15-mg/kg doses of paracetamol at 12-h intervals (paracetamol, paracetamol-glucuronide, paracetamol-sulfate, and the combined oxidative pathway metabolites (paracetamol-cysteine and paracetamol-N-acetylcysteine) were simultaneously modeled in NONMEM 7.2. The model incorporated 259 plasma and 350 urine samples from 35 neonates with a mean gestational age of 33.6 weeks (standard deviation 6.6). CL formation for all metabolites increased with weight; CL formation for glucuronidation and oxidation also increased with postnatal age. At the mean weight (2.3 kg) and postnatal age (7.5 days), CL formation estimates (bootstrap 95% confidence interval; between-subject variability) were 0.049 L/h (0.038-0.062; 62 %) for glucuronidation, 0.21 L/h (0.17-0.24; 33 %) for sulfation, and 0.058 L/h (0.044-0.078; 72 %) for oxidation. Expression of individual oxidation CL formation as a fraction of total individual paracetamol clearance showed that, on average, fractional oxidation CL formation increased paracetamol and its metabolites in neonates. Maturational changes in the fraction of paracetamol undergoing oxidation were small relative to between-subject variability.

  5. Effect of phase interaction on catalytic CO oxidation over the SnO_2/Al_2O_3 model catalyst

    International Nuclear Information System (INIS)

    Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

    2017-01-01

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"4"+ cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn"4"+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  6. Smouldering Combustion of Soil Organic Matter: Inverse Modelling of the Thermal and Oxidative Degradation Kinetics

    Science.gov (United States)

    Huang, Xinyan; Rein, Guillermo

    2013-04-01

    Smouldering combustion of soil organic matter (SOM) such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this work, a kinetic model, including 3-step chemical reactions and 1-step water evaporation is proposed to describe drying, pyrolysis and oxidation behaviour of peat. Peat is chosen as the most important type of SOM susceptible to smoudering, and a Chinese boreal peat sample is selected from the literature. A lumped model of mass loss based on four Arrhenius-type reactions is developed to predict its thermal and oxidative degradation under a range of heating rates. A genetic algorithm is used to solve the inverse problem, and find a group of kinetic and stoichiometric parameters for this peat that provides the best match to the thermogravimetric (TG) data from literature. A multi-objective fitness function is defined using the measurements of both mass loss and mass-loss rate in inert and normal atmospheres under a range of heating rates. Piece-wise optimization is conducted to separate the low temperature drying (450 K). Modelling results shows the proposed 3-step chemistry is the unique simplest scheme to satisfy all given TG data of this particular peat type. Afterward, this kinetic model and its kinetic parameters are incorporated into a simple one-dimensional species model to study the relative position of each reaction inside a smoulder front. Computational results show that the species model agrees with experimental observations. This is the first time that the smouldering kinetics of SOM is explained and predicted, thus helping to understanding this important natural and widespread phenomenon.

  7. Modeling the oxidation of ebselen and other organoselenium compounds using explicit solvent networks.

    Science.gov (United States)

    Bayse, Craig A; Antony, Sonia

    2009-05-14

    The oxidation of dimethylselenide, dimethyldiselenide, S-methylselenenyl-methylmercaptan, and truncated and full models of ebselen (N-phenyl-1,2-benzisoselenazol-3(2H)-one) by methyl hydrogen peroxide has been modeled using density functional theory (DFT) and solvent-assisted proton exchange (SAPE), a method of microsolvation that employs explicit solvent networks to facilitate proton transfer reactions. The calculated activation barriers for these systems were substantially lower in energy (DeltaG(double dagger) + DeltaG(solv) = 13 to 26 kcal/mol) than models that neglect the participation of solvent in proton exchange. The comparison of two- and three-water SAPE networks showed a reduction in the strain in the model system but without a substantial reduction in the activation barriers. Truncating the ebselen model to N-methylisoselenazol-3(2H)-one gave a larger activation barrier than ebselen or N-methyl-1,2-benzisoselenazol-3(2H)-one but provided an efficient means of determining an initial guess for larger transition-state models. The similar barriers obtained for ebselen and Me(2)Se(2) (DeltaG(double dagger) + DeltaG(solv) = 20.65 and 20.40 kcal/mol, respectively) were consistent with experimentally determined rate constants. The activation barrier for MeSeSMe (DeltaG(double dagger) + DeltaG(solv) = 21.25 kcal/mol) was similar to that of ebselen and Me(2)Se(2) despite its significantly lower experimental rate for oxidation of an ebselen selenenyl sulfide by hydrogen peroxide relative to ebselen and ebselen diselenide. The disparity is attributed to intramolecular Se-O interactions, which decrease the nucleophilicity of the selenium center of the selenenyl sulfide.

  8. Mechanistic modelling of a cathode-supported solid oxide fuel cell. Paper no. IGEC-1-103

    International Nuclear Information System (INIS)

    Suwanwarangkul, R.; Croiset, E.; Pritzker, M.D.; Fowler, M.W.; Douglas, P.L.; Entchev, E.

    2005-01-01

    A model for a cathode-supported tubular solid oxide fuel cell operating with humidified H 2 has been developed. Momentum-, mass-, energy- and charge-transport equations coupled with electrochemical reactions (H 2 oxidation and O 2 reduction) are considered in the model. The model also takes into account the radiative heat transfer between the cell and air-preheating tube. The model is validated against published experimental data ands shows a good agreement. The distributions of temperature, current density, reversible cell voltage, overpotential and species mole fractions within the cell are discussed in detail. (author)

  9. Mathematical micro-model of a solid oxide fuel cell composite cathode

    International Nuclear Information System (INIS)

    Kenney, B.; Karan, K.

    2004-01-01

    In a solid oxide fuel cell (SOFC), the cathode processes account for a majority of the overall electrochemical losses. A composite cathode comprising a mixture of ion-conducting electrolyte and electron-conducting electro-catalyst can help minimize cathode losses provided microstructural parameters such as particle-size, composition, and porosity are optimized. The cost of composite cathode research can be greatly reduced by incorporating mathematical models into the development cycle. Incorporated with reliable experimental data, it is possible to conduct a parametric study using a model and the predicted results can be used as guides for component design. Many electrode models treat the cathode process simplistically by considering only the charge-transfer reaction for low overpotentials or the gas-diffusion at high overpotentials. Further, in these models an average property of the cathode internal microstructure is assumed. This paper will outline the development of a 1-dimensional SOFC composite cathode micro-model and the experimental procedures for obtaining accurate parameter estimates. The micro-model considers the details of the cathode microstructure such as porosity, composition and particle-size of the ionic and electronic phases, and their interrelationship to the charge-transfer reaction and mass transport processes. The micro-model will be validated against experimental data to determine its usefulness for performance prediction. (author)

  10. Modeling of Nitrous Oxide Production from Nitritation Reactors Treating Real Anaerobic Digestion Liquor.

    Science.gov (United States)

    Wang, Qilin; Ni, Bing-Jie; Lemaire, Romain; Hao, Xiaodi; Yuan, Zhiguo

    2016-04-29

    In this work, a mathematical model including both ammonium oxidizing bacteria (AOB) and heterotrophic bacteria (HB) is constructed to predict N2O production from the nitritation systems receiving the real anaerobic digestion liquor. This is for the first time that N2O production from such systems was modeled considering both AOB and HB. The model was calibrated and validated using experimental data from both lab- and pilot-scale nitritation reactors. The model predictions matched the dynamic N2O, ammonium, nitrite and chemical oxygen demand data well, supporting the capability of the model. Modeling results indicated that HB are the dominant contributor to N2O production in the above systems with the dissolved oxygen (DO) concentration of 0.5-1.0 mg O2/L, accounting for approximately 75% of N2O production. The modeling results also suggested that the contribution of HB to N2O production decreased with the increasing DO concentrations, from 75% at DO = 0.5 mg O2/L to 25% at DO = 7.0 mg O2/L, with a corresponding increase of the AOB contribution (from 25% to 75%). Similar to HB, the total N2O production rate also decreased dramatically from 0.65 to 0.25 mg N/L/h when DO concentration increased from 0.5 to 7.0 mg O2/L.

  11. Homogeneity of Continuum Model of an Unsteady State Fixed Bed Reactor for Lean CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Subagjo

    2014-07-01

    Full Text Available In this study, the homogeneity of the continuum model of a fixed bed reactor operated in steady state and unsteady state systems for lean CH4 oxidation is investigated. The steady-state fixed bed reactor system was operated under once-through direction, while the unsteady-state fixed bed reactor system was operated under flow reversal. The governing equations consisting of mass and energy balances were solved using the FlexPDE software package, version 6. The model selection is indispensable for an effective calculation since the simulation of a reverse flow reactor is time-consuming. The homogeneous and heterogeneous models for steady state operation gave similar conversions and temperature profiles, with a deviation of 0.12 to 0.14%. For reverse flow operation, the deviations of the continuum models of thepseudo-homogeneous and heterogeneous models were in the range of 25-65%. It is suggested that pseudo-homogeneous models can be applied to steady state systems, whereas heterogeneous models have to be applied to unsteady state systems.

  12. Arsenic mobilization in an oxidizing alkaline groundwater: Experimental studies, comparison and optimization of geochemical modeling parameters

    International Nuclear Information System (INIS)

    Hafeznezami, Saeedreza; Lam, Jacquelyn R.; Xiang, Yang; Reynolds, Matthew D.; Davis, James A.; Lin, Tiffany; Jay, Jennifer A.

    2016-01-01

    Arsenic (As) mobilization and contamination of groundwater affects millions of people worldwide. Progress in developing effective in-situ remediation schemes requires the incorporation of data from laboratory experiments and field samples into calibrated geochemical models. In an oxidizing aquifer where leaching of high pH industrial waste from unlined surface impoundments led to mobilization of naturally occurring As up to 2 mg L −1 , sequential extractions of solid phase As as well as, batch sediment microcosm experiments were conducted to understand As partitioning and solid-phase sorptive and buffering capacity. These data were combined with field data to create a series of geochemical models of the system with modeling programs PHREEQC and FITEQL. Different surface complexation modeling approaches, including component additivity (CA), generalized composite (GC), and a hybrid method were developed, compared and fitted to data from batch acidification experiments to simulate potential remediation scenarios. Several parameters strongly influence the concentration of dissolved As including pH, presence of competing ions (particularly phosphate) and the number of available sorption sites on the aquifer solids. Lowering the pH of groundwater to 7 was found to have a variable, but limited impact (<63%) on decreasing the concentration of dissolved As. The models indicate that in addition to lowering pH, decreasing the concentration of dissolved phosphate and/or increasing the number of available sorption sites could significantly decrease the As solubility to levels below 10 μg L −1 . The hybrid and GC modeling results fit the experimental data well (NRMSE<10%) with reasonable effort and can be implemented in further studies for validation. - Highlights: • Samples were collected from an oxidizing aquifer where high pH waste has led to mobilization of naturally occurring As. • Three surface complexation modeling approaches were used in modeling adsorption

  13. Three job stress models/concepts and oxidative DNA damage in a sample of workers in Japan.

    Science.gov (United States)

    Inoue, Akiomi; Kawakami, Norito; Ishizaki, Masao; Tabata, Masaji; Tsuchiya, Masao; Akiyama, Miki; Kitazume, Akiko; Kuroda, Mitsuyo; Shimazu, Akihito

    2009-04-01

    Three job stress models/concepts (the job demands-control [DC] model, the effort-reward imbalance [ERI] model, and organizational justice) have been linked to coronary heart disease (CHD) at work. In recent years, oxidative DNA damage has been identified as a new risk factor for CHD. However, evidence for the association between these job stressors and oxidative DNA damage is limited. The present cross-sectional study investigated the association between these job stress models/concepts and oxidative DNA damage as a possible mediator of the adverse health effects of job stress. A total of 166 male and 51 female workers of a manufacturing factory in Japan were surveyed using a mailed questionnaire regarding job stressors and demographic, occupational, and lifestyle variables. Urinary concentrations of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of oxidative DNA damage, were also measured. In male subjects, the urinary concentrations of 8-OHdG were significantly higher among the group with lower interactional justice, one of the two components of organizational justice; however, no association was observed with the DC model or the ERI model. In female subjects, high job demands/control ratio was significantly and positively associated with the urinary concentrations of 8-OHdG. Interactional justice among male workers and the DC model-based strain among female workers may be associated with increased urinary concentrations of 8-OHdG which possibly reflects oxidative DNA damage.

  14. Extending the benchmark simulation model no2 with processes for nitrous oxide production and side-stream nitrogen removal

    DEFF Research Database (Denmark)

    Boiocchi, Riccardo; Sin, Gürkan; Gernaey, Krist V.

    2015-01-01

    In this work the Benchmark Simulation Model No.2 is extended with processes for nitrous oxide production and for side-stream partial nitritation/Anammox (PN/A) treatment. For these extensions the Activated Sludge Model for Greenhouse gases No.1 was used to describe the main waterline, whereas...... the Complete Autotrophic Nitrogen Removal (CANR) model was used to describe the side-stream (PN/A) treatment. Comprehensive simulations were performed to assess the extended model. Steady-state simulation results revealed the following: (i) the implementation of a continuous CANR side-stream reactor has...... increased the total nitrogen removal by 10%; (ii) reduced the aeration demand by 16% compared to the base case, and (iii) the activity of ammonia-oxidizing bacteria is most influencing nitrous oxide emissions. The extended model provides a simulation platform to generate, test and compare novel control...

  15. Experimental study and modelling of the high temperature mechanical behavior of oxide dispersion strengthened ferritic steels

    International Nuclear Information System (INIS)

    Steckmeyer, A.

    2012-01-01

    The strength of metals, and therefore their maximum operating temperature, can be improved by oxide dispersion strengthening (ODS). Numerous research studies are carried out at the French Atomic Energy Commission (CEA) in order to develop a cladding tube material for Gen IV nuclear power reactors. Oxide dispersion strengthened steels appear to be the most promising candidates for such application, which demands a minimum operating temperature of 650 C. The present dissertation intends to improve the understanding of the mechanical properties of ODS steels, in terms of creep lifetime and mechanical anisotropy. The methodology of this work includes mechanical tests between room temperature and 900 C as well as macroscopic and polycrystalline modelling. These tests are carried out on a Fe-14Cr1W0,26Ti + 0,3 Y 2 O 3 ODS ferritic steel processed at CEA by mechanical alloying and hot extrusion. The as-received material is a bar with a circular section. The mechanical tests reveal the high mechanical strength of this steel at high temperature. A strong influence of the strain rate on the ductility and the mechanical strength is also observed. A macroscopic mechanical model has been developed on the basis of some experimental statements such as the high kinematic contribution to the flow stress. This model has a strong ability to reproduce the mechanical behaviour of the studied material. Two different polycrystalline models have also been developed in order to reproduce the mechanical anisotropy of the material. They are based on its specific grain morphology and crystallographic texture. The discrepancy between the predictions of both models and experimental results reveal the necessity to formulate alternate assumptions on the deformation mechanisms of ODS ferritic steels. (author) [fr

  16. Oxidative Stress Implications in the Affective Disorders: Main Biomarkers, Animal Models Relevance, Genetic Perspectives, and Antioxidant Approaches.

    Science.gov (United States)

    Balmus, Ioana Miruna; Ciobica, Alin; Antioch, Iulia; Dobrin, Romeo; Timofte, Daniel

    2016-01-01

    The correlation between the affective disorders and the almost ubiquitous pathological oxidative stress can be described in a multifactorial way, as an important mechanism of central nervous system impairment. Whether the obvious changes which occur in oxidative balance of the affective disorders are a part of the constitutive mechanism or a collateral effect yet remains as an interesting question. However it is now clear that oxidative stress is a component of these disorders, being characterized by different aspects in a disease-dependent manner. Still, there are a lot of controversies regarding the relevance of the oxidative stress status in most of the affective disorders and despite the fact that most of the studies are showing that the affective disorders development can be correlated to increased oxidative levels, there are various studies stating that oxidative stress is not linked with the mood changing tendencies. Thus, in this minireview we decided to describe the way in which oxidative stress is involved in the affective disorders development, by focusing on the main oxidative stress markers that could be used mechanistically and therapeutically in these deficiencies, the genetic perspectives, some antioxidant approaches, and the relevance of some animal models studies in this context.

  17. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    Science.gov (United States)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  18. Cardiovascular disease-related parameters and oxidative stress in SHROB rats, a model for metabolic syndrome.

    Directory of Open Access Journals (Sweden)

    Eunice Molinar-Toribio

    Full Text Available SHROB rats have been suggested as a model for metabolic syndrome (MetS as a situation prior to the onset of CVD or type-2 diabetes, but information on descriptive biochemical parameters for this model is limited. Here, we extensively evaluate parameters related to CVD and oxidative stress (OS in SHROB rats. SHROB rats were monitored for 15 weeks and compared to a control group of Wistar rats. Body weight was recorded weekly. At the end of the study, parameters related to CVD and OS were evaluated in plasma, urine and different organs. SHROB rats presented statistically significant differences from Wistar rats in CVD risk factors: total cholesterol, LDL-cholesterol, triglycerides, apoA1, apoB100, abdominal fat, insulin, blood pressure, C-reactive protein, ICAM-1 and PAI-1. In adipose tissue, liver and brain, the endogenous antioxidant systems were activated, yet there was no significant oxidative damage to lipids (MDA or proteins (carbonylation. We conclude that SHROB rats present significant alterations in parameters related to inflammation, endothelial dysfunction, thrombotic activity, insulin resistance and OS measured in plasma as well as enhanced redox defence systems in vital organs that will be useful as markers of MetS and CVD for nutrition interventions.

  19. Remediation of a historically Pb contaminated soil using a model natural Mn oxide waste.

    Science.gov (United States)

    McCann, Clare M; Gray, Neil D; Tourney, Janette; Davenport, Russell J; Wade, Matthew; Finlay, Nina; Hudson-Edwards, Karen A; Johnson, Karen L

    2015-11-01

    A natural Mn oxide (NMO) waste was assessed as an in situ remediation amendment for Pb contaminated sites. The viability of this was investigated using a 10 month lysimeter trial, wherein a historically Pb contaminated soil was amended with a 10% by weight model NMO. The model NMO was found to have a large Pb adsorption capacity (qmax 346±14 mg g(-1)). However, due to the heterogeneous nature of the Pb contamination in the soils (3650.54-9299.79 mg kg(-1)), no treatment related difference in Pb via geochemistry could be detected. To overcome difficulties in traditional geochemical techniques due to pollutant heterogeneity we present a new method for unequivocally proving metal sorption to in situ remediation amendments. The method combines two spectroscopic techniques; namely electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). Using this we showed Pb immobilisation on NMO, which were Pb free prior to their addition to the soils. Amendment of the soil with exogenous Mn oxide had no effect on microbial functioning, nor did it perturb the composition of the dominant phyla. We conclude that NMOs show excellent potential as remediation amendments. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  20. Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

    International Nuclear Information System (INIS)

    Rosselet, C.M.; Kerr, J.A.

    1993-05-01

    During summertime high pressure conditions, high photo-oxidant (O 3 , H 2 O 2 , PAN and others) levels are frequently observed in the planetary boundary layer in central Europe. It is well known that close to the earth's surface ozone is formed by complex reactions involving VOC, NO x , and sunlight. Substantial reductions of both precursors are needed to reduce photo-oxidant levels. In this context the reductions of the abundance of the precursors and the variation of their ratios is of great importance. Here we report model calculations from the Harwell Photochemical Trajectory Model of the levels of O 3 , H 2 O 2 and PAN along a trajectory over the Swiss Plateau from Lake Constance to Lake Geneva. These calculations are in satisfactory agreement with measurements made during the intensive observation period of the research program POLLUMET (Pollution and Meteorology in Switzerland). Sensitivity calculations of emission reduction scenarios indicate that on the Swiss Plateau the ozone production may be mainly NO x -limited; under conditions where the CO levels are closer to the upper limit within the range (120-600 ppbv). The calculated peak ozone level reduction caused by an exclusive NO x -emission reduction is about three times larger than that caused by an exclusive VOC reduction. The combined reduction of all precursor compounds is the most efficient strategy, although it is only marginally more efficient than the NO x -reduction scenario alone. (author) figs., tabs., 75 refs

  1. Selective surface oxidation and segregation upon short term annealing of model alloys and industrial steel grades

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, S.

    2007-07-01

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot-dip galvanizing. This thesis highlights the influence of annealing conditions and the effect of alloying elements on the selective oxidation in model alloys and some industrial steel grades. Model alloys of binary (Fe-2Si, Fe-2Mn, Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr, Fe-1Mn-0.8Cr, Fe-1Si-0.8Cr, Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were studied. In the case of steels, standard grade interstitial free (IF) steels and experimental grade tensile strength 1000 MPa steel were investigated. All specimens were annealed at 820 C in N{sub 2}-5%H{sub 2} gas atmospheres with the wide range of dew points (i.e. -80 to 0 C). The surface chemistry after annealing and its wettability with liquid Zn have been correlated as a function of dew points by simulating the hot-dip galvanizing process at laboratory scale. (orig.)

  2. Intrinsic point defects in zinc oxide. Modeling of structural, electronic, thermodynamic and kinetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Erhart, P.

    2006-07-01

    The present dissertation deals with the modeling of zinc oxide on the atomic scale employing both quantum mechanical as well as atomistic methods. The first part describes quantum mechanical calculations based on density functional theory of intrinsic point defects in ZnO. To begin with, the geometric and electronic structure of vacancies and oxygen interstitials is explored. In equilibrium oxygen interstitials are found to adopt dumbbell and split interstitial configurations in positive and negative charge states, respectively. Semi-empirical self-interaction corrections allow to improve the agreement between the experimental and the calculated band structure significantly; errors due to the limited size of the supercells can be corrected by employing finite-size scaling. The effect of both band structure corrections and finite-size scaling on defect formation enthalpies and transition levels is explored. Finally, transition paths and barriers for the migration of zinc as well as oxygen vacancies and interstitials are determined. The results allow to interpret diffusion experiments and provide a consistent basis for developing models for device simulation. In the second part an interatomic potential for zinc oxide is derived. To this end, the Pontifix computer code is developed which allows to fit analytic bond-order potentials. The code is subsequently employed to obtain interatomic potentials for Zn-O, Zn-Zn, and O-O interactions. To demonstrate the applicability of the potentials, simulations on defect production by ion irradiation are carried out. (orig.)

  3. Kinetic models of controllable pore growth of anodic aluminum oxide membrane

    Science.gov (United States)

    Huang, Yan; Zeng, Hong-yan; Zhao, Ce; Qu, Ye-qing; Zhang, Pin

    2012-06-01

    An anodized Al2O3 (AAO) membrane with apertures about 72 nm in diameter was prepared by two-step anodic oxidation. The appearance and pore arrangement of the AAO membrane were characterized by energy dispersive x-ray spectroscopy and scanning electron microscopy. It was confirmed that the pores with high pore aspect ratio were parallel, well-ordered, and uniform. The kinetics of pores growth in the AAO membrane was derived, and the kinetic models showed that pores stopped developing when the pressure ( σ) trended to equal the surface tension at the end of anodic oxidation. During pore expansion, the effects of the oxalic acid concentration and expansion time on the pore size were investigated, and the kinetic behaviors were explained with two kinetic models derived in this study. They showed that the pore size increased with extended time ( r= G· t+ G'), but decreased with increased concentration ( r = - K·ln c- K') through the derived mathematic formula. Also, the values of G, G', K, and K' were derived from our experimental data.

  4. Comparison of CORA and MELCOR core degradation simulation and the MELCOR oxidation model

    International Nuclear Information System (INIS)

    Wang, Jun; Corradini, Michael L.; Fu, Wen; Haskin, Troy; Tian, Wenxi; Zhang, Yapei; Su, Guanghui; Qiu, Suizheng

    2014-01-01

    Highlights: • Oxidation model of MELCOR is analyzed and the improving suggestion is provided. • MELCOR core degradation calculating results are compared with CORA experiment. • Flow rate of argon and steam, the generating rate of hydrogen is calculated and compared. • Temperature spatial variation and temperature history is calculated and presented. - Abstract: MELCOR is widely used and sufficiently trusted for severe accident analysis. However, the occurrence of Fukushima has increased the focus on severe accident codes and their use. A MELCOR core degradation calculation was conducted at the University of Wisconsin–Madison under the help of Sandia. The calculation results were checked by comparing with a past CORA experiment. MELCOR calculation results included the flow rate of argon and steam, the generation rate of hydrogen. Through this work, the performance of MELCOR COR package was reviewed in detail. This paper compares the hydrogen generation rates predicted by MELCOR to the CORA test data. While agreement is reasonable it could be improved. Additionally, the MELCOR zirconium oxidation model was analyzed

  5. Comparison of CORA and MELCOR core degradation simulation and the MELCOR oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Corradini, Michael L., E-mail: corradini@engr.wisc.edu [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Fu, Wen [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Haskin, Troy [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Tian, Wenxi; Zhang, Yapei; Su, Guanghui; Qiu, Suizheng [State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China)

    2014-09-15

    Highlights: • Oxidation model of MELCOR is analyzed and the improving suggestion is provided. • MELCOR core degradation calculating results are compared with CORA experiment. • Flow rate of argon and steam, the generating rate of hydrogen is calculated and compared. • Temperature spatial variation and temperature history is calculated and presented. - Abstract: MELCOR is widely used and sufficiently trusted for severe accident analysis. However, the occurrence of Fukushima has increased the focus on severe accident codes and their use. A MELCOR core degradation calculation was conducted at the University of Wisconsin–Madison under the help of Sandia. The calculation results were checked by comparing with a past CORA experiment. MELCOR calculation results included the flow rate of argon and steam, the generation rate of hydrogen. Through this work, the performance of MELCOR COR package was reviewed in detail. This paper compares the hydrogen generation rates predicted by MELCOR to the CORA test data. While agreement is reasonable it could be improved. Additionally, the MELCOR zirconium oxidation model was analyzed.

  6. Modeling chemical kinetics of avocado oil ethanolysis catalyzed by solid glycerol-enriched calcium oxide

    International Nuclear Information System (INIS)

    Avhad, M.R.; Sánchez, M.; Bouaid, A.; Martínez, M.; Aracil, J.; Marchetti, J.M.

    2016-01-01

    Highlights: • Raw materials for biodiesel production can be obtained from the natural resources. • The glycerol-enriched CaO catalyst was tested for the ethanolysis of avocado oil. • CaO synthesized through the thermal treatment of Mytilus Galloprovincialis shells. • The ethanol-adsorption step controlled the overall ethanolysis process. • The physico-chemical properties of avocado oil and FAEEs is presented. - Abstract: The catalytic activity of glycerol-enriched calcium oxide for the alcoholysis reaction between avocado oil and ethanol was investigated. The calcium oxide was derived from Mytilus Galloprovincialis shells. This study systematically examined the influence of temperature, ethanol-to-oil molar ratio, and the catalyst amount on the variation in the concentration of triacylglycerols and biodiesel with reaction time. The interaction between the reaction variables (ethanol-to-oil molar ratio and catalyst amount), their influence on the ethanolysis process, and the optimum variables affecting the process were determined through the response surface methodology. A previously developed mathematical model was applied for the current ethanolysis process, and the model parameters were determined. The ethanolysis reaction occurred between the surface chemisorbed ethoxide ions and oil molecules in the liquid phase, while, the overall process was controlled by the ethanol-adsorption step. The physico-chemical properties of biodiesel, produced using potassium methoxide catalyst, were additionally measured.

  7. Annual and seasonal spatial models for nitrogen oxides in Tehran, Iran

    Science.gov (United States)

    Amini, Heresh; Taghavi-Shahri, Seyed-Mahmood; Henderson, Sarah B.; Hosseini, Vahid; Hassankhany, Hossein; Naderi, Maryam; Ahadi, Solmaz; Schindler, Christian; Künzli, Nino; Yunesian, Masud

    2016-09-01

    Very few land use regression (LUR) models have been developed for megacities in low- and middle-income countries, but such models are needed to facilitate epidemiologic research on air pollution. We developed annual and seasonal LUR models for ambient oxides of nitrogen (NO, NO2, and NOX) in the Middle Eastern city of Tehran, Iran, using 2010 data from 23 fixed monitoring stations. A novel systematic algorithm was developed for spatial modeling. The R2 values for the LUR models ranged from 0.69 to 0.78 for NO, 0.64 to 0.75 for NO2, and 0.61 to 0.79 for NOx. The most predictive variables were: distance to the traffic access control zone; distance to primary schools; green space; official areas; bridges; and slope. The annual average concentrations of all pollutants were high, approaching those reported for megacities in Asia. At 1000 randomly-selected locations the correlations between cooler and warmer season estimates were 0.64 for NO, 0.58 for NOX, and 0.30 for NO2. Seasonal differences in spatial patterns of pollution are likely driven by differences in source contributions and meteorology. These models provide a basis for understanding long-term exposures and chronic health effects of air pollution in Tehran, where such research has been limited.

  8. A comprehensive adsorption study and modeling of antibiotics as a pharmaceutical waste by graphene oxide nanosheets.

    Science.gov (United States)

    Rostamian, Rahele; Behnejad, Hassan

    2018-01-01

    The adsorption behavior of tetracycline (TCN), doxycycline (DCN) as the most common antibiotics in veterinary and ciprofloxacin (CPN) onto graphene oxide nanosheets (GOS) in aqueous solution was evaluated. The four factors influencing the adsorption of antibiotics (initial concentration, pH, temperature and contact time) were studied. The results showed that initial pH ∼ 6 to 7 and contact time ∼ 100 - 200min are optimum for each drug. The monolayer adsorption capacity was reduced with the increasing temperature from 25°C to 45°C. Non-linear regressions were carried out in order to define the best fit model for every system. To do this, eight error functions were applied to predict the optimum model. Among various models, Hill and Toth isotherm models represented the equilibrium adsorption data of antibiotics while the kinetic data were well fitted by pseudo second-order (PSO) kinetic model (DCN and TCN) and Elovich (CPN) models. The maximum adsorption capacity (q max ) is found to be in the following order: CPN > DCN > TCN, obtained from sips equation at the same temperature. The GOS shows highest adsorption capacity towards CPN up to 173.4mgg -1 . The study showed that GOS can be removed more efficiently from water solution. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Review on modeling development for multiscale chemical reactions coupled transport phenomena in solid oxide fuel cells

    International Nuclear Information System (INIS)

    Andersson, Martin; Yuan, Jinliang; Sunden, Bengt

    2010-01-01

    A literature study is performed to compile the state-of-the-art, as well as future potential, in SOFC modeling. Principles behind various transport processes such as mass, heat, momentum and charge as well as for electrochemical and internal reforming reactions are described. A deeper investigation is made to find out potentials and challenges using a multiscale approach to model solid oxide fuel cells (SOFCs) and combine the accuracy at microscale with the calculation speed at macroscale to design SOFCs, based on a clear understanding of transport phenomena, chemical reactions and functional requirements. Suitable methods are studied to model SOFCs covering various length scales. Coupling methods between different approaches and length scales by multiscale models are outlined. Multiscale modeling increases the understanding for detailed transport phenomena, and can be used to make a correct decision on the specific design and control of operating conditions. It is expected that the development and production costs will be decreased and the energy efficiency be increased (reducing running cost) as the understanding of complex physical phenomena increases. It is concluded that the connection between numerical modeling and experiments is too rare and also that material parameters in most cases are valid only for standard materials and not for the actual SOFC component microstructures.

  10. Operando X-ray investigation of solid oxide fuel cell model electrodes

    International Nuclear Information System (INIS)

    Volkov, Sergey Aleksandrovic

    2017-04-01

    A detailed study of three solid oxide fuel cells (SOFCs) related model systems is presented in this work with the aim of the better understanding of the structural changes in cell components associated with their operation. The first model system is an La_0_._6Sr_0_._4CoO_3_-_d (LSC) on yttria-stabilized zirconia (YSZ). Changes in the YSZ(100) single crystal surface structure buried under the squared LSC microelectrode were studied at a synchrotron under operational conditions. High flux photon beam at the synchrotron allowed access to the LSC/YSZ interface. Structural information from the substrate surface at an atomic scale was acquired. Element-specific anomalous XRD data allowed to distinguish between Y and Zr scattering contributions. For the first time, it was shown that the Y cation concentration at the electrode/electrolyte interface strongly depends on the sample environment and the applied potential. The second model system is a Pt/YSZ. Buried YSZ(111) surface and dense Pt film morphology changes under operational conditions were addressed. High-energy X-rays were necessary to collect surface-sensitive information from the interface due to highly absorbing Pt film. The main conclusion is - under conditions applied, the YSZ single crystal surface remains stable at an atomic level. A nagging topic of the Pt ''phase oxide'' formation at the Pt/YSZ interface during anodic polarization was also raised. Although XRD data did not show a clear evidence of PtO_x presence at the interface, energy-dispersive X-ray analysis of the film cross-cut profile after the synchrotron experiment revealed distinct oxygen signal from delaminated parts of the film. Last but not least, the structure of a ZrO_2 ultrathin film grown on a Pt_3Zr(0001) single crystal was studied in ultra-high vacuum for the first time be means of SXRD. This model system is aiming to improve understanding of the electrolyte materials based on ZrO_2 (e.g. YSZ) at an atomic level. The results obtained

  11. Operando X-ray investigation of solid oxide fuel cell model electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, Sergey Aleksandrovic

    2017-04-15

    A detailed study of three solid oxide fuel cells (SOFCs) related model systems is presented in this work with the aim of the better understanding of the structural changes in cell components associated with their operation. The first model system is an La{sub 0.6}Sr{sub 0.4}CoO{sub 3-d} (LSC) on yttria-stabilized zirconia (YSZ). Changes in the YSZ(100) single crystal surface structure buried under the squared LSC microelectrode were studied at a synchrotron under operational conditions. High flux photon beam at the synchrotron allowed access to the LSC/YSZ interface. Structural information from the substrate surface at an atomic scale was acquired. Element-specific anomalous XRD data allowed to distinguish between Y and Zr scattering contributions. For the first time, it was shown that the Y cation concentration at the electrode/electrolyte interface strongly depends on the sample environment and the applied potential. The second model system is a Pt/YSZ. Buried YSZ(111) surface and dense Pt film morphology changes under operational conditions were addressed. High-energy X-rays were necessary to collect surface-sensitive information from the interface due to highly absorbing Pt film. The main conclusion is - under conditions applied, the YSZ single crystal surface remains stable at an atomic level. A nagging topic of the Pt ''phase oxide'' formation at the Pt/YSZ interface during anodic polarization was also raised. Although XRD data did not show a clear evidence of PtO{sub x} presence at the interface, energy-dispersive X-ray analysis of the film cross-cut profile after the synchrotron experiment revealed distinct oxygen signal from delaminated parts of the film. Last but not least, the structure of a ZrO{sub 2} ultrathin film grown on a Pt{sub 3}Zr(0001) single crystal was studied in ultra-high vacuum for the first time be means of SXRD. This model system is aiming to improve understanding of the electrolyte materials based on ZrO{sub 2} (e

  12. Boron carbide reinforced aluminium matrix composite: Physical, mechanical characterization and mathematical modelling

    International Nuclear Information System (INIS)

    Shirvanimoghaddam, K.; Khayyam, H.; Abdizadeh, H.; Karbalaei Akbari, M.; Pakseresht, A.H.; Ghasali, E.; Naebe, M.

    2016-01-01

    This paper investigates the manufacturing of aluminium–boron carbide composites using the stir casting method. Mechanical and physical properties tests to obtain hardness, ultimate tensile strength (UTS) and density are performed after solidification of specimens. The results show that hardness and tensile strength of aluminium based composite are higher than monolithic metal. Increasing the volume fraction of B_4C, enhances the tensile strength and hardness of the composite; however over-loading of B_4C caused particle agglomeration, rejection from molten metal and migration to slag. This phenomenon decreases the tensile strength and hardness of the aluminium based composite samples cast at 800 °C. For Al-15 vol% B_4C samples, the ultimate tensile strength and Vickers hardness of the samples that were cast at 1000 °C, are the highest among all composites. To predict the mechanical properties of aluminium matrix composites, two key prediction modelling methods including Neural Network learned by Levenberg–Marquardt Algorithm (NN-LMA) and Thin Plate Spline (TPS) models are constructed based on experimental data. Although the results revealed that both mathematical models of mechanical properties of Al–B_4C are reliable with a high level of accuracy, the TPS models predict the hardness and tensile strength values with less error compared to NN-LMA models.

  13. Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

    Science.gov (United States)

    Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan; Shirzad, Hedayatolah

    2016-01-01

    Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients.

  14. Analytical, 1-Dimensional Impedance Model of a Composite Solid Oxide Fuel Cell Cathode

    DEFF Research Database (Denmark)

    Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

    2014-01-01

    An analytical, 1-dimensional impedance model for a composite solid oxide fuel cell cathode is derived. It includes geometrical parameters of the cathode, e.g., the internal surface area and the electrode thickness, and also material parameters, e.g., the surface reaction rate and the vacancy...... diffusion coefficient. The model is successfully applied to a total of 42 impedance spectra, obtained in the temperature range 555°C–852°C and in the oxygen partial pressure range 0.028 atm–1.00 atm for a cathode consisting of a 50/50 wt% mixture of (La0.6Sr0.4)0.99CoO3 − δ and Ce0.9Gd0.1O1.95 − δ...... and providing both qualitative and quantitative information on the evolution of the impedance spectra of cathodes with changing parameters....

  15. Model of the thermodynamic properties and structure of the non-stoichiometric plutonium and cerium oxides

    International Nuclear Information System (INIS)

    Manes, L.; Mari, C.; Ray, I.

    1979-01-01

    The tetrahedral defect consisting of one oxygen vacancy bonded to two reduced cations - is an important concept, which, as shown in the present work, can explain both the thermodynamic properties and the structures of the phases of the PuO 2 -x and CeO 2 -x systems. Based on this concept a statistical thermodynamic model has been developed and this model is described along with some preliminary calculations. A relatively good agreement with experimental thermodynamic data was obtained in this calculation. Using the exclusion principle, defect complexes each containing one tetrahedral defect are derived and it is shown that a systematic packing of these gives a good description both of the non-stoichiometric and the ordered phases observed for these oxide systems. (orig.) [de

  16. Fenton Process Coupled to Ultrasound and UV Light Irradiation for the Oxidation of a Model Pollutant

    Directory of Open Access Journals (Sweden)

    Karen E. Barrera-Salgado

    2016-01-01

    Full Text Available The Fenton process coupled to photosonolysis (UV light and Us, using Fe2O3 catalyst supported on Al2O3, was used to oxidize a model pollutant like acid green 50 textile dye (AG50. Dye degradation was followed by AG50 concentration decay analyses. It was observed that parameters like iron content on a fixed amount of catalyst supporting material, catalyst annealing temperature, initial dye concentration, and the solution pH influence the overall treatment efficiency. High removal efficiencies of the model pollutant are achieved. The stability and reusability tests of the Fe2O3 catalyst show that the catalyst can be used up to three cycles achieving high discoloration. Thus, this catalyst is highly efficient for the degradation of AG50 in the Fenton process.

  17. Model of porous aluminium oxide growth during initial stage of anodization

    Science.gov (United States)

    Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

    2014-10-01

    Currently, the development of nanotechnology and metamaterials requires the ability to obtain regular self-assembled structures with different parameters. One such structure is porous alumina in which the pores grow perpendicular to the substrate and are hexagonally packed. Pore size and the distance between them can be varied depending on the anodization voltage, the electrolyte and the anodization time (pore diameter - from 2 to 350 nm, the distance between the pores - from 5 to 50 nm). At the moment, there are different models describing the process of anodizing aluminum, in this paper we propose a model that takes into account the effect of layers of aluminum, aluminum oxide, and the electrolyte, as well as the influence of the effect of surface diffusion.

  18. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    International Nuclear Information System (INIS)

    Gelß, Patrick; Matera, Sebastian; Schütte, Christof

    2016-01-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO 2 (110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  19. Modeling of solid oxide fuel cells with particle size and porosity grading in anode electrode

    Energy Technology Data Exchange (ETDEWEB)

    Liu, L.; Flesner, R.; Kim, G.Y.; Chandra, A. [Department of Mechanical Engineering, Iowa State University, Ames, Iowa (United States)

    2012-02-15

    Solid oxide fuel cells (SOFCs) have the potential to meet the critical energy needs of our modern civilization and minimize the adverse environmental impacts from excessive energy consumption. They are highly efficient, clean, and can run on variety of fuel gases. However, little investigative focus has been put on optimal power output based on electrode microstructure. In this work, a complete electrode polarization model of SOFCs has been developed and utilized to analyze the performance of functionally graded anode with different particle size and porosity profiles. The model helps to understand the implications of varying the electrode microstructure from the polarization standpoint. The work identified conditions when grading can improve the cell performance and showed that grading is not always beneficial or necessary. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Science.gov (United States)

    Gelß, Patrick; Matera, Sebastian; Schütte, Christof

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO2(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  1. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Gelß, Patrick, E-mail: p.gelss@fu-berlin.de; Matera, Sebastian, E-mail: matera@math.fu-berlin.de; Schütte, Christof, E-mail: schuette@mi.fu-berlin.de

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO{sub 2}(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  2. An SOA model for toluene oxidation in the presence of inorganic aerosols.

    Science.gov (United States)

    Cao, Gang; Jang, Myoseon

    2010-01-15

    A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene

  3. Modeling on oxide dependent 2DEG sheet charge density and threshold voltage in AlGaN/GaN MOSHEMT

    Science.gov (United States)

    Panda, J.; Jena, K.; Swain, R.; Lenka, T. R.

    2016-04-01

    We have developed a physics based analytical model for the calculation of threshold voltage, two dimensional electron gas (2DEG) density and surface potential for AlGaN/GaN metal oxide semiconductor high electron mobility transistors (MOSHEMT). The developed model includes important parameters like polarization charge density at oxide/AlGaN and AlGaN/GaN interfaces, interfacial defect oxide charges and donor charges at the surface of the AlGaN barrier. The effects of two different gate oxides (Al2O3 and HfO2) are compared for the performance evaluation of the proposed MOSHEMT. The MOSHEMTs with Al2O3 dielectric have an advantage of significant increase in 2DEG up to 1.2 × 1013 cm-2 with an increase in oxide thickness up to 10 nm as compared to HfO2 dielectric MOSHEMT. The surface potential for HfO2 based device decreases from 2 to -1.6 eV within 10 nm of oxide thickness whereas for the Al2O3 based device a sharp transition of surface potential occurs from 2.8 to -8.3 eV. The variation in oxide thickness and gate metal work function of the proposed MOSHEMT shifts the threshold voltage from negative to positive realizing the enhanced mode operation. Further to validate the model, the device is simulated in Silvaco Technology Computer Aided Design (TCAD) showing good agreement with the proposed model results. The accuracy of the developed calculations of the proposed model can be used to develop a complete physics based 2DEG sheet charge density and threshold voltage model for GaN MOSHEMT devices for performance analysis.

  4. Model predictive control of the solid oxide fuel cell stack temperature with models based on experimental data

    Science.gov (United States)

    Pohjoranta, Antti; Halinen, Matias; Pennanen, Jari; Kiviaho, Jari

    2015-03-01

    Generalized predictive control (GPC) is applied to control the maximum temperature in a solid oxide fuel cell (SOFC) stack and the temperature difference over the stack. GPC is a model predictive control method and the models utilized in this work are ARX-type (autoregressive with extra input), multiple input-multiple output, polynomial models that were identified from experimental data obtained from experiments with a complete SOFC system. The proposed control is evaluated by simulation with various input-output combinations, with and without constraints. A comparison with conventional proportional-integral-derivative (PID) control is also made. It is shown that if only the stack maximum temperature is controlled, a standard PID controller can be used to obtain output performance comparable to that obtained with the significantly more complex model predictive controller. However, in order to control the temperature difference over the stack, both the stack minimum and the maximum temperature need to be controlled and this cannot be done with a single PID controller. In such a case the model predictive controller provides a feasible and effective solution.

  5. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1996-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  6. Interaction of Model Inhibitor Compounds with Minimalist Cluster Representations of Hydroxyl Terminated Metal Oxide Surfaces

    Directory of Open Access Journals (Sweden)

    Christopher D. Taylor

    2018-01-01

    Full Text Available The computational modeling of corrosion inhibitors at the level of molecular interactions has been pursued for decades, and recent developments are allowing increasingly realistic models to be developed for inhibitor–inhibitor, inhibitor–solvent and inhibitor–metal interactions. At the same time, there remains a need for simplistic models to be used for the purpose of screening molecules for proposed inhibitor performance. Herein, we apply a reductionist model for metal surfaces consisting of a metal cation with hydroxide ligands and use quantum chemical modeling to approximate the free energy of adsorption for several imidazoline class candidate corrosion inhibitors. The approximation is made using the binding energy and the partition coefficient. As in some previous work, we consider different methods for incorporating solvent and reference systems for the partition coefficient. We compare the findings from this short study with some previous theoretical work on similar systems. The binding energies for the inhibitors to the metal hydroxide clusters are found to be intermediate to the binding energies calculated in other work for bare metal vs. metal oxide surfaces. The method is applied to copper, iron, aluminum and nickel metal systems.

  7. Modelling the descent of nitric oxide during the elevated stratopause event of January 2013

    Science.gov (United States)

    Orsolini, Yvan J.; Limpasuvan, Varavut; Pérot, Kristell; Espy, Patrick; Hibbins, Robert; Lossow, Stefan; Raaholt Larsson, Katarina; Murtagh, Donal

    2017-03-01

    Using simulations with a whole-atmosphere chemistry-climate model nudged by meteorological analyses, global satellite observations of nitrogen oxide (NO) and water vapour by the Sub-Millimetre Radiometer instrument (SMR), of temperature by the Microwave Limb Sounder (MLS), as well as local radar observations, this study examines the recent major stratospheric sudden warming accompanied by an elevated stratopause event (ESE) that occurred in January 2013. We examine dynamical processes during the ESE, including the role of planetary wave, gravity wave and tidal forcing on the initiation of the descent in the mesosphere-lower thermosphere (MLT) and its continuation throughout the mesosphere and stratosphere, as well as the impact of model eddy diffusion. We analyse the transport of NO and find the model underestimates the large descent of NO compared to SMR observations. We demonstrate that the discrepancy arises abruptly in the MLT region at a time when the resolved wave forcing and the planetary wave activity increase, just before the elevated stratopause reforms. The discrepancy persists despite doubling the model eddy diffusion. While the simulations reproduce an enhancement of the semi-diurnal tide following the onset of the 2013 SSW, corroborating new meteor radar observations at high northern latitudes over Trondheim (63.4°N), the modelled tidal contribution to the forcing of the mean meridional circulation and to the descent is a small portion of the resolved wave forcing, and lags it by about ten days.

  8. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T; Jokilaakso, A [Helsinki Univ. of Technology, Otaniemi (Finland)

    1997-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  9. Parameter Identification of the 2-Chlorophenol Oxidation Model Using Improved Differential Search Algorithm

    Directory of Open Access Journals (Sweden)

    Guang-zhou Chen

    2015-01-01

    Full Text Available Parameter identification plays a crucial role for simulating and using model. This paper firstly carried out the sensitivity analysis of the 2-chlorophenol oxidation model in supercritical water using the Monte Carlo method. Then, to address the nonlinearity of the model, two improved differential search (DS algorithms were proposed to carry out the parameter identification of the model. One strategy is to adopt the Latin hypercube sampling method to replace the uniform distribution of initial population; the other is to combine DS with simplex method. The results of sensitivity analysis reveal the sensitivity and the degree of difficulty identified for every model parameter. Furthermore, the posteriori probability distribution of parameters and the collaborative relationship between any two parameters can be obtained. To verify the effectiveness of the improved algorithms, the optimization performance of improved DS in kinetic parameter estimation is studied and compared with that of the basic DS algorithm, differential evolution, artificial bee colony optimization, and quantum-behaved particle swarm optimization. And the experimental results demonstrate that the DS with the Latin hypercube sampling method does not present better performance, while the hybrid methods have the advantages of strong global search ability and local search ability and are more effective than the other algorithms.

  10. Propofol attenuates oxidant-induced acute lung injury in an isolated perfused rabbit-lung model.

    Science.gov (United States)

    Yumoto, Masato; Nishida, Osamu; Nakamura, Fujio; Katsuya, Hirotada

    2005-01-01

    Reactive oxygen species have been strongly implicated in the pathogenesis of acute lung injury (ALI). Some animal studies suggest that free radical scavengers inhibit the onset of oxidant-induced ALI. Propofol (2,6-diisopropylphenol) is chemically similar to phenol-based free radical scavengers such as the endogenous antioxidant vitamin E. Both in vivo and in vitro studies have suggested that propofol has antioxidant potential. We hypothesized that propofol may attenuate ALI by acting as a free-radical scavenger. We investigated the effects of propofol on oxidant-induced ALI induced by purine and xanthine oxidase (XO), in isolated perfused rabbit lung, in two series of experiments. In series 1, we examined the relationship between the severity of ALI and the presence of hydrogen peroxide (H2O2). In series 2, we evaluated the effects of propofol on attenuating ALI and the dose dependence of these effects. The lungs were perfused for 90 min, and we evaluated the effects on the severity of ALI by monitoring the pulmonary capillary filtration coefficient (Kfc), pulmonary arterial pressure (Ppa), and the pulmonary capillary hydrostatic pressure (Ppc). In series 1, treatment with catalase (an H2O2 scavenger) prior to the addition of purine and XO resulted in complete prevention of ALI, suggesting that H2O2 may be involved closely in the pathogenesis of ALI. In series 2, pretreatment with propofol at concentrations in excess of 0.5 mM significantly inhibited the increases in the Kfc values, and that in excess of 0.75 mM significantly inhibited the increase in the Ppa values. Propofol attenuates oxidant-induced ALI in an isolated perfused rabbit lung model, probably due to its antioxidant action.

  11. A lumped model of venting during thermal runaway in a cylindrical lithium cobalt oxide lithium-ion cell

    DEFF Research Database (Denmark)

    Coman, Paul Tiberiu; Rayman, Sean; White, Ralph

    2016-01-01

    This paper presents a mathematical model built for analyzing the intricate thermal behavior of a 18650 LCO (Lithium Cobalt Oxide) battery cell during thermal runaway when venting of the electrolyte and contents of the jelly roll (ejecta) is considered. The model consists of different ODEs (Ordinary...

  12. Empirical study of the metal-nitride-oxide-semiconductor device characteristics deduced from a microscopic model of memory traps

    International Nuclear Information System (INIS)

    Ngai, K.L.; Hsia, Y.

    1982-01-01

    A graded-nitride gate dielectric metal-nitride-oxide-semiconductor (MNOS) memory transistor exhibiting superior device characteristics is presented and analyzed based on a qualitative microscopic model of the memory traps. The model is further reviewed to interpret some generic properties of the MNOS memory transistors including memory window, erase-write speed, and the retention-endurance characteristic features

  13. Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

    Science.gov (United States)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2016-02-01

    Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions

  14. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  15. Short stack modeling of degradation in solid oxide fuel cells. Part II. Sensitivity and interaction analysis

    Science.gov (United States)

    Gazzarri, J. I.; Kesler, O.

    In the first part of this two-paper series, we presented a numerical model of the impedance behaviour of a solid oxide fuel cell (SOFC) aimed at simulating the change in the impedance spectrum induced by contact degradation at the interconnect-electrode, and at the electrode-electrolyte interfaces. The purpose of that investigation was to develop a non-invasive diagnostic technique to identify degradation modes in situ. In the present paper, we appraise the predictive capabilities of the proposed method in terms of its robustness to uncertainties in the input parameters, many of which are very difficult to measure independently. We applied this technique to the degradation modes simulated in Part I, in addition to anode sulfur poisoning. Electrode delamination showed the highest robustness to input parameter variations, followed by interconnect oxidation and interconnect detachment. The most sensitive degradation mode was sulfur poisoning, due to strong parameter interactions. In addition, we simulate several simultaneous two-degradation-mode scenarios, assessing the method's capabilities and limitations for the prediction of electrochemical behaviour of SOFC's undergoing multiple simultaneous degradation modes.

  16. Short stack modeling of degradation in solid oxide fuel cells. Part II. Sensitivity and interaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gazzarri, J.I. [Department of Mechanical Engineering, University of British Columbia, 2054-6250 Applied Science Lane, Vancouver, BC V6T 1Z4 (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, ON M5S 3G8 (Canada)

    2008-01-21

    In the first part of this two-paper series, we presented a numerical model of the impedance behaviour of a solid oxide fuel cell (SOFC) aimed at simulating the change in the impedance spectrum induced by contact degradation at the interconnect-electrode, and at the electrode-electrolyte interfaces. The purpose of that investigation was to develop a non-invasive diagnostic technique to identify degradation modes in situ. In the present paper, we appraise the predictive capabilities of the proposed method in terms of its robustness to uncertainties in the input parameters, many of which are very difficult to measure independently. We applied this technique to the degradation modes simulated in Part I, in addition to anode sulfur poisoning. Electrode delamination showed the highest robustness to input parameter variations, followed by interconnect oxidation and interconnect detachment. The most sensitive degradation mode was sulfur poisoning, due to strong parameter interactions. In addition, we simulate several simultaneous two-degradation-mode scenarios, assessing the method's capabilities and limitations for the prediction of electrochemical behaviour of SOFC's undergoing multiple simultaneous degradation modes. (author)

  17. Dichlone-induced oxidative stress in a model insect species, Spodoptera eridania.

    Science.gov (United States)

    Ahmad, S; Zaman, K; MacGill, R S; Batcabe, J P; Pardini, R S

    1995-11-01

    Southern armyworm, Spodoptera eridania, larvae were provided ad libitum 0.002-0.25% w/w dichlone, 2,3-dichloro-1,4-naphthoquinone (CNQ). Larval mortality occurred in a time-and-dose dependent manner, with an LC17 of 0.01% and an LC50 of 0.26% CNQ at day-5. Extracts of larvae fed control, 0.01, and 0.25% CNQ diets for 5 days were assayed for antioxidant enzymes. While 0.01% CNQ had a mild effect, 0.25% CNQ profoundly increased levels of all antioxidant enzymes that were examined. The increases as compared to control were: 5.3-, 1.9-, 3.2-, 2.6-, 2.8-, and 3.5-fold higher for superoxide dismutase, catalase, glutathione transferase and its peroxidase activity, glutathione reductase and DT-diaphorase, respectively. At 0.01% CNQ, the thiobarbituric acid reactive substances (TBARS) were similar to the control group. However, despite the induction from 0.25% CNQ of all enzymes examined, the lipid peroxidation was not attenuated; the TBARS were 29.7% over the control value. High mortalities and CNQ-induced pathologies reflected in retarded growth, wasting syndrome, and diuresis clearly indicated that the insect sustained severe oxidant-induced injuries before appropriate defenses were fully mobilized. Thus, this quinone causes an oxidative stress in a model insect species analogous to that observed in mammalian species.

  18. A model for the description of oxidation in sulfidic waste rock dumps

    International Nuclear Information System (INIS)

    Bennett, J. W.; Pantelis, G.; Ritchie, A.I.M.; Stepanyants, Y.A.

    2000-03-01

    Basic mathematical equations which describe the processes of sulfide oxidation and gas and water transport in waste rock dumps are presented and discussed. The governing equations account for gas and water flow, vaporisation and condensation with latent heat effects, heat transport and mass balance. Gas, water and solid phases are assumed to be in local thermal equilibrium at all times. Air is approximated as an ideal three-component gas. Different semi-empirical relationships between physical values are used: Darcy's law for fluid flow, ideal gas law, the Van Genuchten formula for the relationship between degree of water saturation and pressure head, Mualem's formula for the relative hydraulic conductivity as a function of pressure head, etc. Some important global quantities, such as the fraction of sulfide sulfur oxidised and the global oxidation rate, are defined and considered as functions of time. The full set of equations is collected and presented in explicit form, convenient for further numerical modelling. The glossary of some technical terms and the table of definitions of the main parameters as well as their units and characteristic values are given

  19. Oxidative stress may be involved in distant organ failure in tourniquet shock model mice.

    Science.gov (United States)

    Nishikata, Rie; Kato, Naho; Hiraiwa, Kouichi

    2014-03-01

    Crush syndrome is characterized by prolonged shock resulting from extensive muscle damage and multiple organ failure. However, the pathogenesis of multiple organ failure has not yet been completely elucidated. Therefore, we investigated the molecular biological and histopathological aspects of distant organ injury in crush syndrome by using tourniquet shock model mice. DNA microarray analysis of the soleus muscle showed an increase in the mRNA levels of Cox-2, Hsp70, c-fos, and IL-6, at 3h after ischemia/reperfusion injury at the lower extremity. In vivo staining with hematoxylin and eosin (HE) showed edema and degeneration in the soleus muscle, but no change in the distant organs. Immunohistological staining of the HSP70 protein revealed nuclear translocation in the soleus muscle, kidney, liver, and lung. The c-fos mRNA levels were elevated in the soleus muscle, kidney, and liver, displaying nuclear translocation of c-FOS protein. Terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL) analysis suggested the involvement of apoptosis in ischemia/reperfusion injury in the soleus muscle. Apoptotic cells were not found in greater quantities in the kidney. Oxidative stress, as determined using a free radical elective evaluator (d-ROM test), markedly increased after ischemia/reperfusion injury. Therefore, examination of immunohistological changes and determination of oxidative stress are proposed to be useful in evaluating the extent of tourniquet shock, even before changes are observed by HE staining. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  20. Non steady-state model for dry oxidation of nuclear wastes metallic containers in long term interim storage conditions

    International Nuclear Information System (INIS)

    Bertrand, Nathalie; Desgranges, Clara; Poquillon, Dominique; Monceau, Daniel

    2006-01-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode. The reason is that, for this kind of waste, the temperature on the surface of the containers will be high enough to avoid any condensation phenomena for several years. Even if the scale growth kinetics is expected to be very slow since the temperature will be moderate at the beginning of the storage (around 300 deg. C) and will keep on decreasing, the metal thickness lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies, performed in the frame of the COCON programme. All existing oxidation models are based on the two main oxidation theories developed by Wagner between the 1930's and 1970's on the one hand, and by Cabrera and Mott in the 1960 and next by Fromhold on the other hand. These used to be associated with high temperature behaviour for Wagner's theory and with low temperature for the second one. Indeed it is certainly more relevant to consider their range of application in terms of the oxide scale thickness rather than in terms of temperature. The question is posed about which theory should an appropriate model rely on. It can be expected that the oxide scale could have a thickness ranging from a few tens of nanometers up to several tens of micrometers depending on temperature and class of alloys chosen. At the present time, low-alloyed steels or carbon steels are considered candidate materials for high-level nuclear waste containers in long term interim storage. For this type of alloys, the scale formed during the dry oxidation stage will be 'rapidly' thick enough to neglect the Mott field. Hence, in a first step, some basic models based on a parabolic rate assumption, that is to say Wagner's model, have been derived from experimental data on iron and on low-alloy steel

  1. Early induction of oxidative stress in mouse model of Alzheimer disease with reduced mitochondrial superoxide dismutase activity.

    Directory of Open Access Journals (Sweden)

    Hyun-Pil Lee

    Full Text Available While oxidative stress has been linked to Alzheimer's disease, the underlying pathophysiological relationship is unclear. To examine this relationship, we induced oxidative stress through the genetic ablation of one copy of mitochondrial antioxidant superoxide dismutase 2 (Sod2 allele in mutant human amyloid precursor protein (hAPP transgenic mice. The brains of young (5-7 months of age and old (25-30 months of age mice with the four genotypes, wild-type (Sod2(+/+, hemizygous Sod2 (Sod2(+/-, hAPP/wild-type (Sod2(+/+, and hAPP/hemizygous (Sod2(+/- were examined to assess levels of oxidative stress markers 4-hydroxy-2-nonenal and heme oxygenase-1. Sod2 reduction in young hAPP mice resulted in significantly increased oxidative stress in the pyramidal neurons of the hippocampus. Interestingly, while differences resulting from hAPP expression or Sod2 reduction were not apparent in the neurons in old mice, oxidative stress was increased in astrocytes in old, but not young hAPP mice with either Sod2(+/+ or Sod2(+/-. Our study shows the specific changes in oxidative stress and the causal relationship with the pathological progression of these mice. These results suggest that the early neuronal susceptibility to oxidative stress in the hAPP/Sod2(+/- mice may contribute to the pathological and behavioral changes seen in this animal model.

  2. The role of phospholipid oxidation products in inflammatory and autoimmune diseases: evidence from animal models and in humans.

    Science.gov (United States)

    Leitinger, Norbert

    2008-01-01

    Since the discovery of oxidized phospholipids (OxPL) and their implication as modulators of inflammation in cardiovascular disease, roles for these lipid oxidation products have been suggested in many other disease settings. Lipid oxidation products accumulate in inflamed and oxidatively damaged tissue, where they are derived from oxidative modification of lipoproteins, but also from membranes of cells undergoing apoptosis. Thus, increased oxidative stress as well as decreased clearance of apoptotic cells has been implied to contribute to accumulation of OxPL in chronically inflamed tissues.A central role for OxPL in disease states associated with dyslipedemia, including atherosclerosis, diabetes and its complications, metabolic syndrome, and renal insufficiency, as well as general prothrombotic states, has been proposed. In addition, in organs which are constantly exposed to oxidative stress, including lung, skin, and eyes, increased levels of OxPL are suggested to contribute to inflammatory conditions. Moreover, accumulation of OxPL causes general immunmodulation and may lead to autoimmune diseases. Evidence is accumulating that OxPL play a role in lupus erythematosus, antiphospholipid syndrome, and rheumatoid arthritis. Last but not least, a role for OxPL in neurological disorders including multiple sclerosis (MS), Alzheimer's and Parkinson's disease has been suggested.This chapter will summarize recent findings obtained in animal models and from studies in humans that indicate that formation of OxPL represents a general mechanism that may play a major role in chronic inflammatory and autoimmune diseases.

  3. Modeling nitrous oxide production and reduction in soil through explicit representation of denitrification enzyme kinetics.

    Science.gov (United States)

    Zheng, Jianqiu; Doskey, Paul V

    2015-02-17

    An enzyme-explicit denitrification model with representations for pre- and de novo synthesized enzymes was developed to improve predictions of nitrous oxide (N2O) accumulations in soil and emissions from the surface. The metabolic model of denitrification is based on dual-substrate utilization and Monod growth kinetics. Enzyme synthesis/activation was incorporated into each sequential reduction step of denitrification to regulate dynamics of the denitrifier population and the active enzyme pool, which controlled the rate function. Parameterizations were developed from observations of the dynamics of N2O production and reduction in soil incubation experiments. The model successfully reproduced the dynamics of N2O and N2 accumulation in the incubations and revealed an important regulatory effect of denitrification enzyme kinetics on the accumulation of denitrification products. Pre-synthesized denitrification enzymes contributed 20, 13, 43, and 62% of N2O that accumulated in 48 h incubations of soil collected from depths of 0-5, 5-10, 10-15, and 15-25 cm, respectively. An enzyme activity function (E) was defined to estimate the relative concentration of active enzymes and variation in response to environmental conditions. The value of E allows for activities of pre-synthesized denitrification enzymes to be differentiated from de novo synthesized enzymes. Incorporating explicit representations of denitrification enzyme kinetics into biogeochemical models is a promising approach for accurately simulating dynamics of the production and reduction of N2O in soils.

  4. Prediction model for oxide thickness on aluminum alloy cladding during irradiation

    International Nuclear Information System (INIS)

    Kim, Yeon Soo; Hofman, G.L.; Hanan, N.A.; Snelgrove, J.L.

    2003-01-01

    An empirical model predicting the oxide film thickness on aluminum alloy cladding during irradiation has been developed as a function of irradiation time, temperature, heat flux, pH, and coolant flow rate. The existing models in the literature are neither consistent among themselves nor fit the measured data very well. They also lack versatility for various reactor situations such as a pH other than 5, high coolant flow rates, and fuel life longer than ∼1200 hrs. Particularly, they were not intended for use in irradiation situations. The newly developed model is applicable to these in-reactor situations as well as ex-reactor tests, and has a more accurate prediction capability. The new model demonstrated with consistent predictions to the measured data of UMUS and SIMONE fuel tests performed in the HFR, Petten, tests results from the ORR, and IRIS tests from the OSIRIS and to the data from the out-of-pile tests available in the literature as well. (author)

  5. Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

    KAUST Repository

    Eldeeb, Mazen A.

    2016-08-30

    A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

  6. Detailed dynamic solid oxide fuel cell modeling for electrochemical impedance spectra simulation

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Ph. [Laboratory of Steam Boilers and Thermal Plants, School of Mechanical Engineering, Thermal Engineering Section, National Technical University of Athens, Heroon Polytechniou 9, 15780 Athens (Greece); Panopoulos, K.D. [Institute for Solid Fuels Technology and Applications, Centre for Research and Technology Hellas, 4th km. Ptolemais-Mpodosakeio Hospital, Region of Kouri, P.O. Box 95, GR 502, 50200 Ptolemais (Greece)

    2010-08-15

    This paper presents a detailed flexible mathematical model for planar solid oxide fuel cells (SOFCs), which allows the simulation of steady-state performance characteristics, i.e. voltage-current density (V-j) curves, and dynamic operation behavior, with a special capability of simulating electrochemical impedance spectroscopy (EIS). The model is based on physico-chemical governing equations coupled with a detailed multi-component gas diffusion mechanism (Dusty-Gas Model (DGM)) and a multi-step heterogeneous reaction mechanism implicitly accounting for the water-gas-shift (WGS), methane reforming and Boudouard reactions. Spatial discretization can be applied for 1D (button-cell approximation) up to quasi-3D (full size anode supported cell in cross-flow configuration) geometries and is resolved with the finite difference method (FDM). The model is built and implemented on the commercially available modeling and simulations platform gPROMS trademark. Different fuels based on hydrogen, methane and syngas with inert diluents are run. The model is applied to demonstrate a detailed analysis of the SOFC inherent losses and their attribution to the EIS. This is achieved by means of a step-by-step analysis of the involved transient processes such as gas conversion in the main gas chambers/channels, gas diffusion through the porous electrodes together with the heterogeneous reactions on the nickel catalyst, and the double-layer current within the electrochemical reaction zone. The model is an important tool for analyzing SOFC performance fundamentals as well as for design and optimization of materials' and operational parameters. (author)

  7. An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

    Science.gov (United States)

    Riedel, T. P.; Wolfe, G. M.; Danas, K. T.; Gilman, J. B.; Kuster, W. C.; Bon, D. M.; Vlasenko, A.; Li, S.-M.; Williams, E. J.; Lerner, B. M.; Veres, P. R.; Roberts, J. M.; Holloway, J. S.; Lefer, B.; Brown, S. S.; Thornton, J. A.

    2014-04-01

    Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm-3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable

  8. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    Science.gov (United States)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  9. Simulating Dynamic Fracture in Oxide Fuel Pellets Using Cohesive Zone Models

    Energy Technology Data Exchange (ETDEWEB)

    R. L. Williamson

    2009-08-01

    It is well known that oxide fuels crack during the first rise to power, with continued fracture occurring during steady operation and especially during power ramps or accidental transients. Fractures have a very strong influence on the stress state in the fuel which, in turn, drives critical phenomena such as fission gas release, fuel creep, and eventual fuel/clad mechanical interaction. Recently, interest has been expressed in discrete fracture methods, such as the cohesive zone approach. Such models are attractive from a mechanistic and physical standpoint, since they reflect the localized nature of cracking. The precise locations where fractures initiate, as well as the crack evolution characteristics, are determined as part of the solution. This paper explores the use of finite element cohesive zone concepts to predict dynamic crack behavior in oxide fuel pellets during power-up, steady operation, and power ramping. The aim of this work is first to provide an assessment of cohesive zone models for application to fuel cracking and explore important numerical issues associated with this fracture approach. A further objective is to provide basic insight into where and when cracks form, how they interact, and how cracking effects the stress field in a fuel pellet. The ABAQUS commercial finite element code, which includes powerful cohesive zone capabilities, was used for this study. Fully-coupled thermo-mechanical behavior is employed, including the effects of thermal expansion, swelling due to solid and gaseous fission products, and thermal creep. Crack initiation is determined by a temperature-dependent maximum stress criterion, based on measured fracture strengths for UO2. Damage evolution is governed by a traction-separation relation, calibrated to data from temperature and burn-up dependent fracture toughness measurements. Numerical models are first developed in 2D based on both axisymmetric (to explore axial cracking) and plane strain (to explore radial

  10. Optical modeling and electrical properties of cadmium oxide nanofilms: Developing a meta–heuristic calculation process model

    Energy Technology Data Exchange (ETDEWEB)

    Abdolahzadeh Ziabari, Ali, E-mail: ali.abd.ziabari@gmail.com [Nano Research Lab, Lahijan Branch, Islamic Azad University, P.O. Box 1616, Lahijan (Iran, Islamic Republic of); Refahi Sheikhani, A. H. [Department of Applied Mathematics, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of); Nezafat, Reza Vatani [Department of Civil Engineering, Faculty of Technology, University of Guilan, Rasht (Iran, Islamic Republic of); Haghighidoust, Kasra Monsef [Department of Mechanical Engineering, Faculty of Technology, University of Guilan, Rasht (Iran, Islamic Republic of)

    2015-04-07

    Cadmium oxide thin films were deposited onto glass substrates by sol–gel dip-coating method and annealed in air. The normal incidence transmittance of the films was measured by a spectrophotometer. D.C electrical parameters such as carrier concentration and mobility were analyzed by Hall Effect measurements. A combination of Forouhi–Bloomer and standard Drude model was used to simulate the optical constants and thicknesses of the films from transmittance data. The transmittance spectra of the films in the visible domain of wavelengths were successfully fitted by using the result of a hybrid particle swarm optimization method and genetic algorithm. The simulated transmittance is in good accordance with the measured spectrum in the whole measurement wavelength range. The electrical parameters obtained from the optical simulation are well consistent with those measured electrically by Hall Effect measurements.

  11. Outcompeting nitrite-oxidizing bacteria in single-stage nitrogen removal in sewage treatment plants: a model-based study.

    Science.gov (United States)

    Pérez, Julio; Lotti, Tommaso; Kleerebezem, Robbert; Picioreanu, Cristian; van Loosdrecht, Mark C M

    2014-12-01

    This model-based study investigated the mechanisms and operational window for efficient repression of nitrite oxidizing bacteria (NOB) in an autotrophic nitrogen removal process. The operation of a continuous single-stage granular sludge process was simulated for nitrogen removal from pretreated sewage at 10 °C. The effects of the residual ammonium concentration were explicitly analyzed with the model. Competition for oxygen between ammonia-oxidizing bacteria (AOB) and NOB was found to be essential for NOB repression even when the suppression of nitrite oxidation is assisted by nitrite reduction by anammox (AMX). The nitrite half-saturation coefficient of NOB and AMX proved non-sensitive for the model output. The maximum specific growth rate of AMX bacteria proved a sensitive process parameter, because higher rates would provide a competitive advantage for AMX. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. 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

  13. Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover.

    Science.gov (United States)

    Feng, S; Ng, C W W; Leung, A K; Liu, H W

    2017-10-01

    Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

  14. Mathematical modeling of the radiation-chemical oxidation of U(IV) in HClO4

    International Nuclear Information System (INIS)

    Vladimirova, M.V.

    1995-01-01

    Mathematical modeling of U(IV) oxidation in 0.5-12 M HClO 4 upon α, γ-radiolysis, based on the proposed scheme of radiation-chemical reactions, has been performed. The rate constants of the U(VI) + HO 2 , U(IV) + HO 2 , U(IV) + ClO 2 , and U(IV) + ClO 2 - reactions have been determined by the comparison of the calculated and experimental kinetic and dose curves and radiation-chemical yields of U(IV) oxidation or U(VI) formation. General equations for uranium (IV) oxidation constants at various HClO 4 concentrations, based on the analysis of the rates of particular radiation-chemical reactions composing oxidation process, have been obtained

  15. Watson-Crick Base Pair Radical Cation as a Model for Oxidative Damage in DNA.

    Science.gov (United States)

    Feketeová, Linda; Chan, Bun; Khairallah, George N; Steinmetz, Vincent; Maitre, Philippe; Radom, Leo; O'Hair, Richard A J

    2017-07-06

    The deleterious cellular effects of ionizing radiation are well-known, but the mechanisms causing DNA damage are poorly understood. The accepted molecular events involve initial oxidation and deprotonation at guanine sites, triggering hydrogen atom abstraction reactions from the sugar moieties, causing DNA strand breaks. Probing the chemistry of the initially formed radical cation has been challenging. Here, we generate, spectroscopically characterize, and examine the reactivity of the Watson-Crick nucleobase pair radical cation in the gas phase. We observe rich chemistry, including proton transfer between the bases and propagation of the radical site in deoxyguanosine from the base to the sugar, thus rupturing the sugar. This first example of a gas-phase model system providing molecular-level details on the chemistry of an ionized DNA base pair paves the way toward a more complete understanding of molecular processes induced by radiation. It also highlights the role of radical propagation in chemistry, biology, and nanotechnology.

  16. Experimental and kinetic modeling study of C2H4 oxidation at high pressure

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  17. Intermediate Co/Ni-base model superalloys — Thermophysical properties, creep and oxidation

    International Nuclear Information System (INIS)

    Zenk, Christopher H.; Neumeier, Steffen; Engl, Nicole M.; Fries, Suzana G.; Dolotko, Oleksandr; Weiser, Martin; Virtanen, Sannakaisa; Göken, Mathias

    2016-01-01

    The mechanical properties of γ′-strengthened Co–Ni–Al–W–Cr model superalloys extending from pure Ni-base to pure Co-base superalloys have been assessed. Differential scanning calorimetry measurements and thermodynamic calculations match well and show that the γ′ solvus temperature decreases with increasing Co-content. The γ/γ′ lattice misfit is negative on the Ni- and positive on the Co-rich side. High Ni-contents decelerate the oxidation kinetics up to a factor of 15. The creep strength of the Ni-base alloy increases by an order of magnitude with additions of Co before it deteriorates strongly upon higher additions despite an increasing γ′ volume fraction.

  18. Modelling and control of solid oxide fuel cell generation system in microgrid

    Science.gov (United States)

    Zhou, Niancheng; Li, Chunyan; Sun, Fangqing; Wang, Qianggang

    2017-11-01

    Compared with other kinds of fuel cells, solid oxide fuel cell (SOFC) has been widely used in microgrids because of its higher efficiency and longer operation life. The weakness of SOFC lies in its slow response speed when grid disturbance occurs. This paper presents a control strategy that can promote the response speed and limit the fault current impulse for SOFC systems integrated into microgrids. First, the hysteretic control of the bidirectional DC-DC converter, which joins the SOFC and DC bus together, is explored. In addition, an improved droop control with limited current protection is applied in the DC-AC inverter, and the active synchronization control is applied to ensure a smooth transition of the microgrid between the grid-connected mode and the islanded mode. To validate the effectiveness of this control strategy, the control model was built and simulated in PSCAD/EMTDC.

  19. Alzheimer's Proteins, Oxidative Stress, and Mitochondrial Dysfunction Interplay in a Neuronal Model of Alzheimer's Disease

    Directory of Open Access Journals (Sweden)

    Antonella Bobba

    2010-01-01

    Full Text Available In this paper, we discuss the interplay between beta-amyloid (A peptide, Tau fragments, oxidative stress, and mitochondria in the neuronal model of cerebellar granule neurons (CGNs in which the molecular events reminiscent of AD are activated. The identification of the death route and the cause/effect relationships between the events leading to death could be helpful to manage the progression of apoptosis in neurodegeneration and to define antiapoptotic treatments acting on precocious steps of the death process. Mitochondrial dysfunction is among the earliest events linked to AD and might play a causative role in disease onset and progression. Recent studies on CGNs have shown that adenine nucleotide translocator (ANT impairment, due to interaction with toxic N-ter Tau fragment, contributes in a significant manner to bioenergetic failure and mitochondrial dysfunction. These findings open a window for new therapeutic strategies aimed at preserving and/or improving mitochondrial function.

  20. First-Principles Modeling of ThO2 Solid Solutions with Oxides of Trivalent Cations

    Science.gov (United States)

    Alexandrov, Vitaly; Asta, Mark; Gronbech-Jensen, Niels

    2010-03-01

    Solid solutions formed by doping ThO2 with oxides of trivalent cations, such as Y2O3 and La2O3, are suitable for solid electrolyte applications, similar to doped zirconia and ceria. ThO2 has also been gaining much attention as an alternative to UO2 in nuclear energy applications, the aforementioned trivalent cations being important fission products. In both cases the mixing energetics and short-range ordering/clustering are key to understanding structural and transport properties. Using first-principles atomistic calculations, we address intra- and intersublattice interactions for both cation and anion sublattices in ThO2-based fluorite-type solid solutions and compare the results with similar modeling studies for related trivalent-doped zirconia systems.

  1. A kinetic model of the oxidative dissolution of brannerite, UTi2O6

    International Nuclear Information System (INIS)

    Thomas, B.S.; Zhang, Y.

    2003-01-01

    The aqueous dissolution of synthetic brannerite (UTi 2 O 6 ) in an open atmosphere has been investigated. Previous data in the literature have been combined with new experimental work, dealing with the release of uranium from brannerite as a function of solution pH and aqueous carbonate species, in oxygenated solutions. From these data we have developed a conceptual model for uranium release from brannerite consisting of two reaction steps: oxidation of surface uranium(IV) atoms, and subsequent detachment of U(VI) atoms into solution, which is catalysed by surface coordination with protons (acidic media) or carbonate species (alkaline media in equilibrium with the atmosphere). A kinetic rate law is derived for this simple reaction mechanism and fitted to experimental data. The resulting predictive equation for uranium release qualitatively describes the pH-dependent behaviour observed in experiment, and quantitatively gives an upper limit for uranium release from brannerite over a range of conditions and experiment types. (orig.)

  2. Lithium-Vanadium bronzes as model catalysts for the selective reduction of nitric oxide

    NARCIS (Netherlands)

    Bosch, H.; Bongers, Annemie; Enoch, Gert; Snel, Ruud; Ross, Julian R.H.

    1989-01-01

    The effect of alkali metals on the selective reduction of nitric oxide with ammonia has been studied on bulk iron oxide and bulk vanadium oxide. The influence of additions of LiOH, NaOH and KOH on the