WorldWideScience

Sample records for b4c oxidation modelling

  1. Validierung und Verbesserung des Programmsystems ATHLET-CD hinsichtlich der B4C-Oxidation in Dampfatmosphäre

    OpenAIRE

    Drath, Tilman

    2007-01-01

    In Leichtwasserreaktoren kann es während eines postulierten Kühlmittelverluststörfalls bei gleichzeitigem Ausfall aller Sicherheitssysteme zum Ausdampfen des Primärsystems und damit zur Kernaufheizung und -zerstörung kommen. Dabei stellen exotherme Oxidationsvorgänge in Dampf ein wesentliches Phänomen dar, da sie die Aufheizung zusätzlich beschleunigen und zum H2-Quellterm beitragen. Im Gegensatz zur Oxidation des Hüllrohrwerkstoffs Zirkon werden bei der Oxidation des Absorbermate...

  2. Experimental investigation on mechanical behaviour, modelling and optimization of wear parameters of B4C and graphite reinforced aluminium hybrid composites

    International Nuclear Information System (INIS)

    Highlights: • Aluminium alloy reinforced with boron carbide and graphite through liquid casting. • The high hardness and elongation obtained in the AA 7075 hybrid composite. • SEM, EDS observations were used to evaluate the worn surface. • MINITAB software was used to analyse the wear rate and develop the map. - Abstract: Aluminium alloy (AA) 6061 and 7075 were reinforced with 10 wt.% of boron carbide (B4C) and 5 wt.% of graphite through liquid casting technique. The Scanning Electron Microscope (SEM) and Energy Dispersive Spectrum (EDS) were used for the characterization of composites. The wear experiment was carried out by using a pin-on-disc apparatus with various input parameters like applied load (10, 20, and 30 N), sliding speed (0.6, 0.8, and 1.0 m/s) and sliding distance (1000, 1500, and 2000 m). Response Surface Methodology (RSM) using MINITAB 14 software was used to analyse the wear rate of hybrid composites and aluminium alloys. The worn surfaces of hybrid composites and base alloys were studied through SEM and EDS systems and some useful conclusions were made

  3. X-ray properties and interface study of B4C/Mo and B4C/Mo2C periodic multilayers

    Science.gov (United States)

    Choueikani, F.; Bridou, F.; Lagarde, B.; Meltchakov, E.; Polack, F.; Mercere, P.; Delmotte, F.

    2013-04-01

    We present a comparative study of B4C/Mo and B4C/Mo2C periodic multilayer structures deposited by magnetron sputtering. The characterization was performed by grazing incidence X-ray reflectometry at two different energies and high resolution transmission electron microscopy. The experimental results indicate the existence of an interdiffusion layer at the B4C-on-Mo interface in the B4C/Mo system. Thus, the B4C/Mo multilayers were modeled by an asymmetric structure with three layers in each period. The thickness of B4C-on-Mo interfacial layer was estimated about 1.1 nm. The B4C/Mo2C multilayers present less interdiffusion and are well modeled by a symmetric structure without interfacial layers. This study shows that B4C/Mo2C structure is an interesting alternative to B4C/Mo multilayer for X-ray optic applications.

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

    International Nuclear Information System (INIS)

    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

  5. 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.

  6. B4C thin films for neutron detection

    OpenAIRE

    Höglund, Carina; Birch, Jens; Andersen, Ken; Bigault, Thierry; Buffet, Jean-Claude; Correa, Jonathan; Van Esch, Patrick; Guerard, Bruno; Hall-Wilton, Richard; Jensen, Jens; Khaplanov, Anton; Piscitelli, Francesco; Vettier, Christian; Vollenberg, Wilhelmus; Hultman, Lars

    2012-01-01

    Due to the very limited availability of He-3, new kinds of neutron detectors, not based on 3He, are urgently needed. Here, we present a method to produce thin films of (B4C)-B-10, with maximized detection efficiency, intended to be part of a new generation of large area neutron detectors. B4C thin Films have been deposited onto Al-blade and Si wafer substrates by dc magnetron sputtering from (B4C)-B-nat and (B4C)-B-10 targets in an Ar discharge, using an industrial deposition system. The film...

  7. Retention of deuterium implanted into B4C-overlaid isotropic graphites and hot-pressed B4C

    International Nuclear Information System (INIS)

    Retention characteristics of two kinds of B4C-overlaid graphites and hot-pressed B4C were investigated. An ion beam of 3 keV D2+ was implanted into the specimens at room temperature. The amount of retained deuteriums was measured as function of the implantation fluence and temperature by elastic recoil detection analysis. Thermal release behavior of implanted deuteriums was also measured by isochronal annealing. The concentration of retained deuterium reaches saturation similarly in three kinds of B4C-overlaid specimens at the fluences over 1018 D+/cm2 as in isotropic graphite. The release temperature, at which the number of retained deuterium decreases to one half in isochronal annealing are about 250 K lower for three kinds of B4C specimens than for graphite. The release temperature of deuterium from unsaturated hot-pressed B4C isochronal annealing is about 500 K higher than that from saturated one. (orig.)

  8. Boron carbide (B4C) coating. Deposition and testing

    Science.gov (United States)

    Azizov, E.; Barsuk, V.; Begrambekov, L.; Buzhinsky, O.; Evsin, A.; Gordeev, A.; Grunin, A.; Klimov, N.; Kurnaev, V.; Mazul, I.; Otroshchenko, V.; Putric, A.; Sadovskiy, Ya.; Shigin, P.; Vergazov, S.; Zakharov, A.

    2015-08-01

    Boron carbide was proposed as a material of in-situ protecting coating for tungsten tiles of ITER divertor. To prove this concept the project including investigation of regimes of plasma deposition of B4C coating on tungsten and tests of boron carbide layer in ITER-like is started recently. The paper contends the first results of the project. The results of B4C coating irradiation by the plasma pulses of QSPU-T plasma accelerator are presented. The new device capable of B4C film deposition on tungsten and testing of the films and materials with ITER-like heat loads and ion- and electron irradiation is described. The results of B4C coating deposition and testing of both tungsten substrate and coating are shown and discussed.

  9. B4C thin films for neutron detection

    International Nuclear Information System (INIS)

    Due to the very limited availability of 3He, new kinds of neutron detectors, not based on 3He, are urgently needed. Here, we present a method to produce thin films of 10B4C, with maximized detection efficiency, intended to be part of a new generation of large area neutron detectors. B4C thin films have been deposited onto Al-blade and Si wafer substrates by dc magnetron sputtering from natB4C and 10B4C targets in an Ar discharge, using an industrial deposition system. The films were characterized with scanning electron microscopy, elastic recoil detection analysis, x-ray reflectivity, and neutron radiography. We show that the film-substrate adhesion and film purity are improved by increased substrate temperature and deposition rate. A deposition rate of 3.8 A/s and substrate temperature of 400 deg. C result in films with a density close to bulk values and good adhesion to film thickness above 3 μm. Boron-10 contents of almost 80 at. % are obtained in 6.3 m2 of 1 μm thick 10B4C thin films coated on Al-blades. Initial neutron absorption measurements agree with Monte Carlo simulations and show that the layer thickness, number of layers, neutron wavelength, and amount of impurities are determining factors. The study also shows the importance of having uniform layer thicknesses over large areas, which for a full-scale detector could be in total ∼1000 m2 of two-side coated Al-blades with ∼1 μm thick 10B4C films.

  10. Reaction behavior between B4C, 304 grade of stainless steel and Zircaloy at 1473 K

    Science.gov (United States)

    Sasaki, Ryosuke; Ueda, Shigeru; Kim, Sun-Joong; Gao, Xu; Kitamura, Shin-ya

    2016-08-01

    For a better understanding of the decommissioning of the Fukushima-daiichi nuclear power plant, the melting behavior of the control blade and the channel box should be clarified. In Fukushima nuclear reactor, the channel box was made of Zircaloy-4, and the control rode is made of B4C together with stainless steel cladding and sheath. In the study, the interaction among B4C, stainless steel (SUS), and Zircaloy-4 was investigated at 1473 K in either argon or air atmosphere. In argon, Zircaloy is melted by the diffusion of elements from SUS, and SUS was melted at 1473 K by the diffusion of C and B. In air, SUS reacted with B2O3 and formed an oxides melt firstly. Then, the oxidized Zircaloy contacted with this melt and fused. Moreover, the progress of core melting process during severe accident under different atmospheres was firstly discussed.

  11. Microstructure and mechanical properties of pulsed electric current sintered B4C-TiB2 composites

    International Nuclear Information System (INIS)

    Research highlights: → Fast densification of B4C-TiB2 particulate composites. → Oxide impurity removal by evaporation. → Judiciously controlled loading cycle during pulsed electric current sintering. → High strength micrometer sized B4C-TiB2 composites. - Abstract: Monolithic B4C, TiB2 and B4C-TiB2 particulate composites were consolidated without sintering additives by means of pulsed electric current sintering in vacuum. Sintering studies on B4C-TiB2 composites were carried out to reveal the influence of the pressure loading cycle during pulsed electrical current sintering (PECS) on the removal of oxide impurities, i.e. boron oxide and titanium oxide, hereby influencing the densification behavior as well as microstructure evolvement. The critical temperature to evaporate the boron oxide impurities was determined to be 2000 deg. C. Fully dense B4C-TiB2 composites were achieved by PECS for 4 min at 2000 deg. C when applying the maximum external pressure of 60 MPa after volatilization of the oxide impurities, whereas a relative density of 95-97% was obtained when applying the external pressure below 2000 deg. C. Microstructural analysis showed that B4C and TiB2 grain growth was substantially suppressed due to the pinning effect of the secondary phase and the rapid sintering cycle, resulting in micrometer sized and homogeneous microstructures. Excellent properties were obtained for the 60 vol% TiB2 composite, combining a Vickers hardness of 29 GPa, a fracture toughness of 4.5 MPa m1/2 and a flexural strength of 867 MPa, as well as electrical conductivity of 3.39E+6 S/m.

  12. Characteristics of electrodeposited RE-Ni-W-B-B4C-MoS2 composite coating

    Institute of Scientific and Technical Information of China (English)

    马克毅; 郭忠诚; 朱晓云; 徐瑞东

    2003-01-01

    The high temperature oxidation resistance of RE-Ni-W-B-B4C-MoS2 composite coating, the effects of electrodeposition conditions on the morphologies of the coating and the effect of heat treatment temperature on its hardness, abrasion resistance and phase structure were investigated by using scanning electron microscope(SEM), X-ray diffractometer, microhardness tester and abrasion machine. The results show that the oxidation degree of RE-Ni-W-B-B4C-MoS2 composite coating is small when the temperature is lower than 700 ℃, but it increases sharply when the temperature is higher than 700 ℃. The hardness of RE-Ni-W-B-B4C-MoS2 composite coating increases with increasing heat treatment temperature, it comes up to the maximum value at 400 ℃,but it decreases gradually if the temperature rises continuously. The most favourable abrasion resistance was attained after RE-Ni-W-B-B4C-MoS2 composite coating being heat treated at 400 ℃. Without heat treating, it is mainly amorphous and partially crystallized, but wholly crystallized after being heat treated at 500 ℃. RE in the composite coating is in the form of CeO2 and additions of CeO2 and B4C can enhance the thermostability of RE-Ni-W-B-B4C-MoS2 composite coating.

  13. Interfacial properties and electron structure of Al/B4C interface: A first-principles study

    Science.gov (United States)

    Xian, Yajiang; Qiu, Ruizhi; Wang, Xin; Zhang, Pengcheng

    2016-09-01

    This research aims at investigating the structural, mechanical and electronic properties of the Al (111)/B4C (0001) interface by first-principles calculations. This model geometry Al (111)/B4C (0001) is chosen because the close-packed planes of Al and B4C have the (111) and (0001) orientation, respectively, and the lattice mismatch is only ∼2.1%. Among four B4C (0001) surfaces with different terminations, our calculation of surface free energies predicted that C-terminated B4C (0001) surface is the most stable one. Relaxed atomic geometries, the work of adhesion and interfacial free energies were calculated for three C-terminated B4C (0001)/Al (111) interfaces with different stacking sequences (top-site, hollow-site, and bridge-site). Results reveal that the relaxed top-site (hollow-site-like) Al/B4C interface has the best adhesion force and also be the most stable. The interfacial electron structure including charge density difference, Bader charge and density of states (DOS) is analyzed to determine the nature of metal/carbide bonding and we find the formation of Alsbnd C bond and possibly the formation of Al4C3 in the interface.

  14. Cr/B4C multilayer mirrors: Study of interfaces and X-ray reflectance

    Science.gov (United States)

    Burcklen, C.; Soufli, R.; Dennetiere, D.; Polack, F.; Capitanio, B.; Gullikson, E.; Meltchakov, E.; Thomasset, M.; Jérome, A.; de Rossi, S.; Delmotte, F.

    2016-03-01

    We present an experimental study of the effect of layer interfaces on the x-ray reflectance in Cr/B4C multilayer interference coatings with layer thicknesses ranging from 0.7 nm to 5.4 nm. The multilayers were deposited by magnetron sputtering and by ion beam sputtering. Grazing incidence x-ray reflectometry, soft x-ray reflectometry, and transmission electron microscopy reveal asymmetric multilayer structures with a larger B4C-on-Cr interface, which we modeled with a 1-1.5 nm thick interfacial layer. Reflectance measurements in the vicinity of the Cr L2,3 absorption edge demonstrate fine structure that is not predicted by simulations using the currently tabulated refractive index (optical constants) values for Cr.

  15. Chemical State Mapping of Degraded B4C Control Rod Investigated with Soft X-ray Emission Spectrometer in Electron Probe Micro-analysis

    Science.gov (United States)

    Kasada, R.; Ha, Y.; Higuchi, T.; Sakamoto, K.

    2016-05-01

    B4C is widely used as control rods in light water reactors, such as the Fukushima Daiichi nuclear power plant, because it shows excellent neutron absorption and has a high melting point. However, B4C can melt at lower temperatures owing to eutectic interactions with stainless steel and can even evaporate by reacting with high-temperature steam under severe accident conditions. To reduce the risk of recriticality, a precise understanding of the location and chemical state of B in the melt core is necessary. Here we show that a novel soft X-ray emission spectrometer in electron probe microanalysis can help to obtain a chemical state map of B in a modeled control rod after a high-temperature steam oxidation test.

  16. 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)

    The effect of the Ti/B4C mole ratio on the fabrication behavior of Al composites is investigated using Al–Ti–B4C 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, TiB2 is formed in all the samples whereas TiC is only formed in reactants with a Ti/B4C mole ratio of more than two. The C atoms from the reacted B4C do not move into TiC but instead they move into Al3BC or Al4C3 when the Ti/B4C mole ratio is less than two. In addition, the reaction mechanism with a Ti/B4C mole ratio of 0.75 is investigated extensively. - Highlights: • The critical role of the Ti/B4C mole ratio on the reaction products of Al–Ti–B4C was studied using experiments. • The experimental results are also supported by thermodynamic calculations presented in this paper. • The reaction mechanism with a Ti/B4C mole ratio of 0.75 is investigated extensively

  17. Comparison of nanostructured Al/B4C composite produced by ARB and Al/B4C composite produced by RRB process

    International Nuclear Information System (INIS)

    Research highlights: → The SEM microstructures revealed the well distributed B4C particles in the aluminum matrix for both the composites. → The TEM analysis showed the nanostructured Al/B4C composite was produced by the ARB process successfully. → The ductility (elongation) of the RRB processed composite is higher than that of the ARB processed composite. → The microhardness of the ARB processed composite is higher than that of the RRB processed composite. - Abstract: In the present study, Al/B4C composites were produced and compared in the form of sheets, through accumulative roll bonding (ARB) and repeated roll bonding (RRB) processes. The microstructure of the composites fabricated by both the methods, revealed by scanning electron microscopy (SEM), showed the B4C particles properly distributed in the aluminum matrix. The average grain size of the ARB processed composite was about 186 nm by linear intercept method, based on transmission electron microscopy (TEM) observations. Mechanical properties of the Al/B4C composites produced by two methods were investigated by tensile and hardness tests. The results showed that the tensile strength and hardness of the ARB and RRB processed composites increase with the number of cycles. However, the tensile strength and hardness of the ARB processed composite are much higher than those of the RRB processed composite. The tensile test results revealed that the elongation of the ARB processed composite is lower than that of the RRB processed composite.

  18. Study on the Blistering of B4C/Al Neutron Absorber Plate in the Course of Corrosion%B4C/Al中子吸收板腐蚀过程中的起泡研究

    Institute of Scientific and Technical Information of China (English)

    李刚; 王美玲; 王贯春; 简敏

    2012-01-01

    The corrosion model of cladding blistering on B4C/A1 neutron absorber plate was established by Henry's law, and by means of the model to investigate the relationship between pore radius and temperature factors for blistering. Influence of pore size for the neutron absorber plate blistering was analyzed by using the pore capillary effects. The results show that the hydrogen pressure produced in small radius pores is higher due to Al corrosion, which contributed to B4C/A1 neutron absorber plate cladding blistering. Influence of temperature on the corrosion generated hydrogen pressure is very small, but the main factors affecting the hydrogen pressure is the pore radius sizes. Blistering power of the cladding is hydrogen continuous generation and accumulating in the pore capillary. The water diffuses easily through the pore capillary in B4C/A1 cores, which will cause the cladding blistering because of Al corrosion.%根据亨利定律,建立了B4C/Al中子吸收板包壳腐蚀起泡的模型,计算了孔隙半径、温度对起泡的影响,并利用孔隙毛细管效应分析了孔隙对中子吸收板起泡的影响.结果表明:孔隙半径越小,腐蚀产生的氢气压力越大,B4C/Al中子吸收板包壳更易起泡;温度对腐蚀产生的氢气压力影响非常小,而孔隙半径是影响氢气压力的主要因素;氢气持续产生并在孔隙毛细管中积聚,是包壳产生起泡的动力;水分容易通过孔隙毛细管在B4C/Al芯体中扩散,可导致Al腐蚀,引起包壳起泡.

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

    International Nuclear Information System (INIS)

    The preparation, physical and mechanical properties of Al/ B4C composites with 5 and 10 wt.% reinforcement content were investigated. In order to obtain the feedstock with a low powder loading, B4C 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/ B4C composites prepared by powder metallurgy was high. (Author)

  20. Microstructure and Tensile Behaviour of B4C Reinforced ZA43 Alloy Composites

    Science.gov (United States)

    Adaveesh, B.; Halesh, G. M.; Nagaral, Madeva; Mohan Kumar, T. S.

    2016-09-01

    The work is carried out to investigate and study the mechanical properties of B4C reinforced ZA43 alloy metal matrix composites. In the present work ZA43 alloy is taken as the base matrix and B4C particulates as reinforcement material to prepare metal matrix composites by stir casting method. For metal matrix composites the reinforcement material was varied from 0 to 6 wt.% in steps of 3 wt.%. For each composite, the reinforcement particulates were preheated to a temperature of 300°C and dispersed into a vortex of molten ZA43 alloy. The microstructural characterization was done using scanning electron microscope. Mechanical properties like hardness, ultimate tensile strength and yield strength were evaluated as per ASTM standards. Further, scanning electron microphotographs revealed that there was uniform distribution of B4C particulates in ZA43 alloy matrix. Hardness, ultimate tensile strength and yield strength increased as wt.% of B4C increased in the base matrix.

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

    International Nuclear Information System (INIS)

    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/cm3) gives in the final product a weight approximately 30% lower than armor made of alumina (3.96 g/cm3). (author)

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

    International Nuclear Information System (INIS)

    Highlights: • Preparation of B4C and BN nanopowders using a simple ball milling process. • Homogeneous dispersion and strong adhesion of nano-B4C 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 (B4C) 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

  3. The design, fabrication and properties of B4C/Al neutron absorbers

    International Nuclear Information System (INIS)

    Neutron absorber is used for the criticality safety during the storage or transportation of spent nuclear fuel. In this work, the metal matrix composite with good mechanical property and thermal neutron absorbing ability was investigated based on B4C/Al neutron radiation shielding material. The composition ratio for B4C/Al composite was firstly designed and the dependence of the neutron transmission on the thickness of the material was calculated. By vacuum hot-pressing technique at a low temperature, the neutron absorbers with high concentration of B4C were fabricated. Furthermore, the corresponding microstructure, physical, mechanical and corrosion properties as well as fracture surface were analyzed, proving that the developed composites can shield the neutron radiation as effectively as cadmium materials

  4. Electrochemical Behavior of Al-B4C Metal Matrix Composites in NaCl Solution

    Directory of Open Access Journals (Sweden)

    Yu-Mei Han

    2015-09-01

    Full Text Available Aluminum based metal matrix composites (MMCs have received considerable attention in the automotive, aerospace and nuclear industries. One of the main challenges using Al-based MMCs is the influence of the reinforcement particles on the corrosion resistance. In the present study, the corrosion behavior of Al-B4C MMCs in a 3.5 wt.% NaCl solution were investigated using potentiodynamic polarization (PDP and electrochemical impedance spectroscopy (EIS techniques. Results indicated that the corrosion resistance of the composites decreased when increasing the B4C volume fraction. Al-B4C composite was susceptible to pitting corrosion and two types of pits were observed on the composite surface. The corrosion mechanism of the composite in the NaCl solution was primarily controlled by oxygen diffusion in the solution. In addition, the galvanic couples that formed between Al matrix and B4C particles could also be responsible for the lower corrosion resistance of the composites.

  5. Tribological behavior of liquid metallurgy-processed AA 6061-B4C composites

    International Nuclear Information System (INIS)

    Aluminum metal matrix composites (AMMCs) possess improved properties compared to their monolithic counterparts and serve as a reliable alternative to replace them for applications that are considered as their niche. In the present investigation, 6061 Al alloy-10 wt% B4C composite is fabricated through liquid metallurgy stir casting technique and analyzed for its tribological characteristics. The uniform distribution of B4C reinforcement particles in the composite is achieved by the above route and is characterized using microstructure analysis and x-ray diffraction spectrum. The dry wear tests have been conducted under ambient conditions using a pin-on-disc tribometer. The worn surface and debris of the composite are also characterized using a scanning electron microscope (SEM) and energy-dispersive x-ray spectroscopy (EDS). It is found that the combination of adhesion, delamination and abrasion constitute the predominant wear mechanism and this is influenced by the B4C particles, applied load, sliding distance and speed. The wear and friction coefficient increase with increase in applied load for all the load conditions studied. While the sliding speed fosters the engendering of a mechanically mixed layer (MML) to reduce the wear and friction coefficient, in contrast, the increase in sliding distance scuttles the MML formation owing to abrasion induced by the hard B4C particles. (paper)

  6. Mechanical Properties and Strengthening Mechanisms of Al-15 Pct B4C Composites with Sc and Zr at Elevated Temperatures

    Science.gov (United States)

    Qin, Jian; Zhang, Zhan; Chen, X.-Grant

    2016-09-01

    The mechanical properties at ambient and elevated temperatures of two Al-15 vol pct B4C composites, S40 with 0.4 wt pct Sc and SZ40 with 0.4 wt pct Sc and 0.24 wt pct Zr, are investigated during long-term thermal annealing. The presence of large B4C particles in the microscale has a moderate but stable strengthening effect on Al-B4C composites at ambient and elevated temperatures, while the precipitation of nanoscale Al3Sc and Al3(Sc, Zr) in the composite matrix provides a predominate contribution to the composite strength, which is varied by tested temperatures. The Al3Sc precipitates in S40 remain coarsening resistant at 523 K (250 °C), whereas the Al3(Sc, Zr) precipitates in SZ40 are thermally stable at 573 K (300 °C) over 2000 hours of annealing. At higher annealing temperatures (573 K (300 °C) for S40 and 623 K (350 °C) for SZ40), both Al3Sc and Al3(Sc, Zr) precipitates become coarsening with prolonged annealing time. The yield strength of S40 and SZ40 at ambient temperature decreases with the increasing precipitate size, which can be explained by the classical precipitate shearing and Orowan bypass mechanisms. At elevated temperatures [523 K to 623 K (250 °C to 350 °C)], considerably lower yield stresses are observed compared to those at ambient temperature, which invokes a dislocation climb mechanism. The predicted yield strengths at elevated temperatures by the combination of dislocation climb and Orowan models are in good agreement with the experimental data.

  7. Determination of Optimum Cutting Parameters for Surface Roughness in Turning AL-B4C Composites

    Science.gov (United States)

    Channabasavaraja, H. K.; Nagaraj, P. M.; Srinivasan, D.

    2016-09-01

    Many materials such as alloys, composites find their applications on the basis of machinability, cost and availability. In the present work, machinability of Aluminium 1100 and Boron carbide (AL+ B4C) composite material is examined by using lathe tool dynometers (BANKA Lathe) by varying the cutting parameters like spindle speed, Depth of cut and Feed rate in 3 levels. Also, surface roughness is measured against the weight % of reinforcement in the composite (0, 4 and 8 %). From the study it is observed that the hardness of a composite material increases with increase in weight % of reinforcement material (B4C) by 26.27 and 66.7 % respectively. The addition of reinforcement materials influences the machinability. The cutting force in both X and Z direction were also found increment with the reinforcement percentage.

  8. Chemical compatibility of sodium exposed alloy D9 with B4C

    International Nuclear Information System (INIS)

    The control rods in India's first prototype fast breeder reactor (PFBR) would consist of high-density B4C (containing 67% 10B isotope) pellets enclosed in alloy D9 clad tubes. Enriched boron carbide required for control rod applications in PFBR is being produced indigenously by reacting elemental boron with graphite at high temperatures. The gap between the control rod material and the clad is filled with liquid sodium as the pins are of vented type. At the reactor operating temperatures of 773-873 K, the chemical interaction between B4C and D9 clad material surface modified by liquid sodium needs to be investigated and understood. Towards this, out-of-pile accelerated chemical compatibility experiments were carried out and the SEM/EDS, XRD and XPS results of the studies carried out at 973 K for 5000 h are presented in this paper

  9. Consolidation of B4C-TaB2 eutectic composites by spark plasma sintering

    OpenAIRE

    Dmytro Demirskyi

    2015-01-01

    The in situ synthesis/consolidation of B4C-TaB2 eutectic composites by spark plasma sintering (SPS) is reported. The microstructure–property relations were determined for composites with the B4C-TaB2 eutectic composition as functions of TaB2 content, and TaB2-TaB2 interlamellar spacing. A clear maximum in fracture toughness was identified (∼4.5 MPa m1/2) for eutectic composites with interlamellar spacing between 0.9 and 1.1 μm. The composites with the hypereutectic composition of 40 mol.% TaB...

  10. 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.

  11. Laser controlled melting of HSLA steel surface with presence of B4C particles

    Science.gov (United States)

    Yilbas, B. S.; Patel, F.; Karatas, C.

    2013-10-01

    Laser gas assisted melting of high strength low alloy steel surface is carried out. The alloy surface is pre-prepared to contain 5% B4C particles in a 40 μm thick carbon film prior to laser treatment process. Metallurgical and morphological changes in the laser treated layer are examined by using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. The residual stress developed and the microhardness of the resulting surface is measured. It is found that B4C particles remain in solid phase in the surface region due to their high melting temperature. The dense layer consisting of fine grains are formed at the surface and the feathery like structure is observed below the surface vicinity, which consists of martensite and nitride precipitations. The use of nitrogen at high pressure causes the formation of nitride compounds at the surface, which contributes to the volume shrinkage in the dense layer. Surface microhardness increases considerably because of attainment of high cooling rates, formation of nitride compounds, and presence of B4C particles at the surface.

  12. Preparation and investigation of Al–4 wt% B4C nanocomposite powders using mechanical milling

    Indian Academy of Sciences (India)

    A Alizadeh; E Taheri-Nassaj; H R Baharvandi

    2011-08-01

    Boron carbide nanoparticles were produced using commercially available boron carbide powder (0.8 m).Mechanical milling was used to synthesize Al nanostructured powder in a planetary ball-mill under argon atmosphere up to 20 h. The same process was applied for Al–4 wt% B4C nanocomposite powders to explore the role of nanosize reinforcements on mechanical milling stages. Scanning electron microscopy (SEM) analysis as well as apparent density measurements were used to optimize the milling time needed for completion of the mechanical milling process. The results show that the addition of boron carbide particles accelerate the milling process, leading to a faster work hardening rate and fracture of aluminum matrix. FE-SEM images show that distribution of boron carbide particles in aluminum matrix reaches a full homogeneity when steady state takes place. The better distribution of reinforcement throughout the matrix would increase hardness of the powder. To study the compressibility of milled powder, modified heckel equation was used to consider the pressure effect on yield strength as well as reinforcing role of B4C particles. For better distribution of reinforcement throughout the matrix, , modified heckel equation was used to consider the pressure effect on yield strength as well as reinforcing role of B4C particles.

  13. Evolution of reinforcement distribution in Al-B4C composites during accumulative roll bonding

    International Nuclear Information System (INIS)

    Highlights: → ARB developed a nanostructure in the matrix of the Al-B4C composite. → An improvement in the reinforcement distribution was found by increasing ARB passes. → By progression of ARB from one to seven passes, hardness increased from 60 to 82 HV. -- Abstract: The distribution of reinforcement particles in the matrix of a composite is one of the most important microstructural features affecting properties. In this study, nanostructured Al-B4C composite sheets were processed by accumulative roll bonding (ARB), and the effect of the number of ARB cycles on the distribution of the B4C particles in the Al matrix was evaluated. From optical microscopic studies accompanied by the radial distribution function analysis, it was realized that the microstructure uniformity is improved by increasing the number of ARB cycles. It was in good agreement with bulk hardness measurements in which the standard deviation of the hardness values was decreased by progression of the ARB process. In addition, the X-ray diffraction peak profile analysis revealed that the area weighted mean crystallite size of the Al matrix decreases to the nanometric scale (114 nm) after seven ARB cycles.

  14. Preparation and characterization of B4C coatings for advanced research light sources.

    Science.gov (United States)

    Störmer, Michael; Siewert, Frank; Sinn, Harald

    2016-01-01

    X-ray optical elements are required for beam transport at the current and upcoming free-electron lasers and synchrotron sources. An X-ray mirror is a combination of a substrate and a coating. The demand for large mirrors with single layers consisting of light or heavy elements has increased during the last few decades; surface finishing technology is currently able to process mirror lengths up to 1 m with microroughness at the sub-nanometre level. Additionally, thin-film fabrication is able to deposit a suitable single-layer material, such as boron carbide (B4C), some tens of nanometres thick. After deposition, the mirror should provide excellent X-ray optical properties with respect to coating thickness errors, microroughness values and slope errors; thereby enabling the mirror to transport the X-ray beam with high reflectivity, high beam flux and an undistorted wavefront to an experimental station. At the European XFEL, the technical specifications of the future mirrors are extraordinarily challenging. The acceptable shape error of the mirrors is below 2 nm along the whole length of 1 m. At the Helmholtz-Zentrum Geesthacht (HZG), amorphous layers of boron carbide with thicknesses in the range 30-60 nm were fabricated using the HZG sputtering facility, which is able to cover areas up to 1500 mm long by 120 mm wide in one step using rectangular B4C sputtering targets. The available deposition area is suitable for the specified X-ray mirror dimensions of upcoming advanced research light sources such as the European XFEL. The coatings produced were investigated by means of X-ray reflectometry and interference microscopy. The experimental results for the B4C layers are discussed according to thickness uniformity, density, microroughness and thermal stability. The variation of layer thickness in the tangential and sagittal directions was investigated in order to estimate the achieved level of uniformity over the whole deposition area, which is considerably

  15. Preparation and characterization of B4C coatings for advanced research light sources

    Science.gov (United States)

    Störmer, Michael; Siewert, Frank; Sinn, Harald

    2016-01-01

    X-ray optical elements are required for beam transport at the current and upcoming free-electron lasers and synchrotron sources. An X-ray mirror is a combination of a substrate and a coating. The demand for large mirrors with single layers consisting of light or heavy elements has increased during the last few decades; surface finishing technology is currently able to process mirror lengths up to 1 m with microroughness at the sub-nanometre level. Additionally, thin-film fabrication is able to deposit a suitable single-layer material, such as boron carbide (B4C), some tens of nanometres thick. After deposition, the mirror should provide excellent X-ray optical properties with respect to coating thickness errors, microroughness values and slope errors; thereby enabling the mirror to transport the X-ray beam with high reflectivity, high beam flux and an undistorted wavefront to an experimental station. At the European XFEL, the technical specifications of the future mirrors are extraordinarily challenging. The acceptable shape error of the mirrors is below 2 nm along the whole length of 1 m. At the Helmholtz-Zentrum Geesthacht (HZG), amorphous layers of boron carbide with thicknesses in the range 30–60 nm were fabricated using the HZG sputtering facility, which is able to cover areas up to 1500 mm long by 120 mm wide in one step using rectangular B4C sputtering targets. The available deposition area is suitable for the specified X-ray mirror dimensions of upcoming advanced research light sources such as the European XFEL. The coatings produced were investigated by means of X-ray reflectometry and interference microscopy. The experimental results for the B4C layers are discussed according to thickness uniformity, density, microroughness and thermal stability. The variation of layer thickness in the tangential and sagittal directions was investigated in order to estimate the achieved level of uniformity over the whole deposition area, which is

  16. Stability and normal incidence reflectivity of W/B4C multilayer mirror near the boron K absorption edge.

    Science.gov (United States)

    Rao, P N; Rai, S K; Nayak, M; Lodha, G S

    2013-09-01

    A multilayer structure consisting of alternate layers of W and B4C has been deposited using a magnetron sputtering system. The structure of the as-deposited and vacuum-annealed W/B4C multilayer sample has been characterized using grazing incidence x-ray reflectivity, grazing incidence diffraction, and the normal incidence reflectivity has been measured using synchrotron radiation. A two-layer model consisting of tungsten and boron carbide is presented. The multilayer structure was found to be stable after 800°C annealing. Grazing incidence x-ray diffraction measurements suggested that W is polycrystalline with small grain size. No signature of tungsten carbide or tungsten boride formation could be observed during the annealing treatments. A near normal incidence soft x-ray reflectivity (SXRR) of ~8.3% was obtained at 6.8 nm wavelength. A little drop (~1%) in SXRR after 800°C annealing suggested that there were no compositional changes within the layers during the annealing treatments.

  17. Consolidation of B4C-TaB2 eutectic composites by spark plasma sintering

    Directory of Open Access Journals (Sweden)

    Dmytro Demirskyi

    2015-12-01

    Full Text Available The in situ synthesis/consolidation of B4C-TaB2 eutectic composites by spark plasma sintering (SPS is reported. The microstructure–property relations were determined for composites with the B4C-TaB2 eutectic composition as functions of TaB2 content, and TaB2-TaB2 interlamellar spacing. A clear maximum in fracture toughness was identified (∼4.5 MPa m1/2 for eutectic composites with interlamellar spacing between 0.9 and 1.1 μm. The composites with the hypereutectic composition of 40 mol.% TaB2 obtained by SPS exhibited lower Vickers hardness (25–26 GPa but higher indentation fracture toughness (up to 4.9 MPa m1/2 than eutectic composites with 30–35 mol.% of TaB2.

  18. Helium bubble evolution in ion irradiated Al/B4C metal matrix composite

    International Nuclear Information System (INIS)

    Graphical abstract: Scheme of combined irradiation includes a pre-implantation of 400 keV He+ to 1.0 × 1016 ions/cm2 followed by a 1.5 MeV proton irradiation to 2.2 × 1019 ions/cm2 on the perpendicular surface. TEM samples were prepared by FIB. The area suffered with both He+ pre-implantation and proton irradiation was marked as light blue. - Abstract: Helium behavior in Al/B4C metal matrix composite with two different sets of ion irradiation conditions has been investigated by transmission electron microscopy. Helium bubbles in Al were found to be much larger than those in B4C after a helium fluence of 1.5 × 1017 ions/cm2 at the room temperature. Also, bubbles at grain boundaries and their vicinity in aluminum are faceted. With additional proton irradiation, a bubble denuded zone along the aluminum grain boundary appears. The results are discussed in terms of the energetics of the material system

  19. Optical properties of boron carbide near the boron K edge evaluated by soft-x-ray reflectometry from a Ru/B(4)C multilayer.

    Science.gov (United States)

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

    2009-12-10

    Soft-x-ray Bragg reflection from two Ru/B(4)C multilayers with 10 and 63 periods was used for independent determination of both real and imaginary parts of the refractive index n = 1 - delta + ibeta close to the boron K edge (approximately 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 B(4)C and various boron oxides.

  20. Ballistic Impact Behavior of Nacre-Like Laminated Composites Consisting of B4C Tablets and Polyurea Matrix

    Science.gov (United States)

    Grujicic, M.; Snipes, J. S.; Ramaswami, S.

    2016-03-01

    A nacre-like composite armor consisting of B4C tablets and polyurea matrix is modeled, and its ballistic impact behavior and penetration resistance (under a normal and a 15°-oblique impact by a solid right circular cylindrical projectile) were analyzed using a series of transient, nonlinear dynamic, finite-element analyses. Nacre is a biological material constituting the innermost layer of the shells of gastropods and bivalves. It consists of polygonal tablets of aragonite, tessellated to form individual layers and having the adjacent layers as well as the tablets within a layer bonded by a biopolymer. Due to its highly complex hierarchical microstructure, nacre possesses an outstanding combination of mechanical properties, the properties which are far superior to the ones that are predicted using the homogenization techniques such as the rule of mixtures. The results of the transient nonlinear dynamic analysis pertaining to the ballistic impact response and the penetration resistance of the modeled nacre-like armor are compared with their counterparts for the B4C single-block armor having an identical areal density. Furthermore, the effect of various nacre microstructural features (e.g., surface profiling, micron-scale asperities, mineral bridges between the overlapping tablets lying in adjacent layers) on the ballistic penetration resistance of the nacre-like composite armor is investigated in order to identify an optimal nacre-like composite-armor architecture having the largest penetration resistance. The results obtained clearly show that a nacre-like armor possesses a superior penetration resistance relative to its monolithic counterpart, and that the nacre microstructural features considered play a critical role in the armor penetration resistance.

  1. Dry Sliding Tribological Studies of AA6061-B4C-Gr Hybrid Composites

    Science.gov (United States)

    Monikandan, V. V.; Joseph, M. A.; Rajendrakumar, P. K.

    2016-10-01

    The dry sliding behavior of stir-cast AA6061-10 wt.% B4C composites containing 2.5, 5 and 7.5 wt.% graphite particles was studied as a function of applied load, sliding speed and sliding distance on a pin-on-disk tribotester. The wear rate and friction coefficient increased with increase in applied load and sliding distance. The increase in graphite addition reduced the increase in wear rate and friction coefficient in the sliding speed range 2-2.5 m/s. Scanning electron microscopy of the worn pin revealed a graphite tribolayer, and transmission electron microscopy revealed overlapping deformation bands under 30 N applied load. Upon increasing the applied load to 40 N, welded region with fine crystalline structure was formed due to dynamic recrystallization of AA6061 alloy matrix.

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

    International Nuclear Information System (INIS)

    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. B4C 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

  3. Processing and characterization of B4C/Cu graded composite as plasma facing component for fusion reactors

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new approach for fabricating B4C/Cu graded composite by rapid self-resistance sintering under ultra-high pressure was presented, by which a near dense B4C/Cu graded composite with a compositional spectrum of 0-100% was successfully fabricated. Plasma relevant performances ofsintered B4C/Cu composite were preliminarily characterized, it is found that its chemical sputtering yield is 70% lower than that of SMF800 nuclear graphite under 2.7 keV D+ irradiation, and almost no damages after 66 shots of in situ plasma discharge in HL-1 Tokamak facility, which indicates B4C/Cu plasma facing component has a good physical and chemical sputtering resistance performance compared with nuclear graphite.

  4. Fabrication of Al5083/B4C surface composite by friction stir processing and its tribological characterization

    OpenAIRE

    Narayana Yuvaraj; Sivanandam Aravindan; Vipin

    2015-01-01

    Improved surface properties with the retainment of bulk properties are necessary for a component for enhanced wear characteristics. Friction stir processing (FSP) is used to produce such surface composites. Fabrication of 5083 aluminum alloy with reinforced layers of boron carbide (B4C) through FSP was carried out. Micro and nano sized B4C particles were used as reinforcements. The friction processed surface composite layer was analyzed through optical and scanning electron microscopical stud...

  5. Microstructure and Dry-Sliding Wear Behavior of B4C Ceramic Particulate Reinforced Al 5083 Matrix Composite

    Directory of Open Access Journals (Sweden)

    Qian Zhao

    2016-09-01

    Full Text Available B4C ceramic particulate–reinforced Al 5083 matrix composite with various B4C content was fabricated successfully via hot-press sintering under Argon atmosphere. B4C particles presented relative high wettability, bonding strength and symmetrical distribution in the Al 5083 matrix. The hardness value, friction coefficient and wear resistance of the composite were higher than those of the Al 5083 matrix. The augment of the B4C content resulted in the increase of the friction coefficient and decrease of the wear mass loss, respectively. The 30 wt % B4C/Al 5083 composite exhibited the highest wear resistance. At a low load of 50 N, the dominant wear mechanisms of the B4C/Al 5083 composite were micro-cutting and abrasive wear. At a high load of 200 N, the dominant wear mechanisms were micro-cutting and adhesion wear associated with the formation of the delamination layer which protected the composite from further wear and enhanced the wear resistance under the condition of high load.

  6. Phase Constitution in Mixed Gd2O3 and B4C by Sintering at High Temperature

    Institute of Scientific and Technical Information of China (English)

    Wu Wenyuan; Xu Jingyu; Bian Xue; Hu Guangyong; Sun Shuchen; Tu Ganfeng

    2005-01-01

    The phase constitution in mixed Gd2O3 and B4C by sintering in graphite tube furnace at the temperature of 100~1489 ℃ in argon atmosphere was studied by means of XRD and TG-DTA. The results show that the impurity C reacts with O in the B4C at the temperature of 367~458 ℃. When the temperature is 800 ℃, Gd2O3 reacts with B4C, and the reaction products include GdB6, GdB4, GdBO3, GdBC and B. GdBC changes into GdB4 at 1200 ℃. When the temperature is 1470 ℃, GdB6 is obtained by the reaction of GdB4 with elemental B. The content of GdB6 is increasing with the prolonging time.

  7. Fabrication and Properties of SiB6-B4C with Phenolic Resin as a Carbon Source

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Si-B-C ceramic composites were synthesized using SiB6, B4C, and phenolic resin as a carbon source by pressureless sintering in an Ar atmosphere. Then, the Si-B-C ceramic composites were fabricated to determine their potential for applications as high hardness and high temperature composites. The X-ray diffraction patterns of sintered bodies of SiB6-B4C with carbonized phenolic resin can be seen that SiB6 and C changed to B4C and SiC. In this study, it is obtained that carbonized phenolic resin is good addition material as a reaction material comparing to carbon powder at 1683 K for 1 h by pressureless sintering in an Ar atmosphere.

  8. Structure and characteristics of electrodeposited RE-Ni-W-P-B4C-PTFE composite coatings

    Institute of Scientific and Technical Information of China (English)

    陈凌; 郭忠诚; 杨显万

    2001-01-01

    Hardness, friction and wear characteristics of electrodeposited RE-Ni-W-P-B4C-PTFE composite coatings were studied, and the reason for these fine characteristics was explained in respect of structure. The results show that 1)the structure of RE-Ni-W-P-B4C-PTFE composite coatings experiences a transformation process from amorphous to mixture then to crystal as the heat-treatment temperature rises; 2) incorporating of B4C greatly increases the hardness of the coating; 3) the wear resistance of the coating is best with heat-treatment for 1 h at 300 ℃, which is greatly superior to that of the other traditional coatings.

  9. Resonant soft x-ray reflectivity of Me/B(4)C multilayers near the boron K edge.

    Science.gov (United States)

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich

    2010-09-01

    Energy dependence of the optical constants of boron carbide in the short period Ru/B(4)C and Mo/B(4)C 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 B(4)Cmaterial 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/B(4)C ML with narrow barrier layers appears as a homogeneous ML at all energies, a Ru/B(4)C 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 186eV, we found an enriched concentration of metallic boron inside the Ru-rich layer at the surface, which is not visible in other energy ranges.

  10. A W:B4C multilayer phase retarder for broadband polarization analysis of soft x-ray radiation

    NARCIS (Netherlands)

    MacDonald, Michael A.; Schaefers, Franz; Pohl, R.; Poole, Ian B.; Gaupp, Andreas; Quinn, Frances M.

    2008-01-01

    A W:B4C multilayer phase retarder has been designed and characterized which shows a nearly constant phase retardance between 640 and 850 eV photon energies when operated near the Bragg condition. This freestanding transmission multilayer was used successfully to determine, for the first time, the fu

  11. High reflectance Cr/V multilayer with B(4)C barrier layer for water window wavelength region.

    Science.gov (United States)

    Huang, Qiushi; Fei, Jiani; Liu, Yang; Li, Pin; Wen, Mingwu; Xie, Chun; Jonnard, Philippe; Giglia, Angelo; Zhang, Zhong; Wang, Kun; Wang, Zhanshan

    2016-02-15

    To develop the high reflectance mirror for the short wavelength range of the water window region (λ=2.42-2.73  nm), Cr/V multilayers with B4C barrier layers are studied. The grazing incidence x-ray reflectometry results show that the multilayer interface widths are significantly reduced down to 0.21-0.31 nm, after the introduction of 0.1 nm B4C barrier layers at both interfaces. The [B4C/Cr/B4C/V] multilayer with a large number of bilayers of N=300 maintains the same small interface widths while the surface roughness is only 0.2 nm. According to the transmission electron microscope measurements, the layer structure improvement with barrier layers can be attributed to the suppression of the crystallization of vanadium inside the structure. Using the interface engineered multilayer, a maximum soft x-ray reflectance of 24.3% is achieved at λ=2.441  nm, under the grazing incidence of 42°. PMID:26872167

  12. Neutron irradiation tests on B4C/epoxy composite for neutron shielding application and the parameters assay

    Science.gov (United States)

    Adeli, Ruhollah; Shirmardi, Seyed Pezhman; Ahmadi, Seyed Javad

    2016-10-01

    In this investigation, epoxy resin with a low viscosity amine-based curing agent was chosen as matrix and additives were added to epoxy resin using low speed stirring with ultrasonic waves approach. The chemical stability of resin during fabrication of composites was studied with Fourier transform infrared spectroscopy (FTIR). The effect of B4C particle size (20 and 150 μm) on neutron shielding was investigated. Besides, in order to develop the high performance composites, the effect of ATH (flame retardant) and WO3 powders (for shielding from against gamma rays) on neutron shielding property is considered. The neutron experiments were based on foil activation analysis in thermal column of Tehran Research Reactor (TRR). According to experimental data, required shield thickness (B4C, 150 μm, 3 wt%) for 80% absorption of neutron fluence was calculated about 9.8 mm. Consequently, data show thermal neutron absorption is dependent also on the size of the boron compound filler and show a significant enhancement in shielding performance when using smaller particle size of B4C filler. Furthermore, data obviously show that the neutron attenuation coefficient of reinforced composites increases to 0.345 cm-1 for B4C (20 μm, 5 wt%)/ Epoxy composite shield. As clearly data indicate, adding WO3 and ATH additive had a significant influence on the thermal neutron attenuation property and hybrid shield shows an enhancement of more than 60% in shielding performance.

  13. Study of multi-carbide B4C-SiC/(Al, Si) reaction infiltrated composites by SEM with EBSD

    International Nuclear Information System (INIS)

    In the definition of conceptual developments and design of new materials with singular or unique properties, characterisation takes a key role in clarifying the relationships of composition, properties and processing that define the new material. B4C has a rare combination of properties that makes it suitable for a wide range of applications in engineering: high refractoriness, thermal stability, high hardness and abrasion resistance coupled to low density. However, the low self-diffusion coefficient of B4C limits full densification by sintering. A way to overturn this constraint is by using an alloy, for example Al-Si, forming composites with B4C. Multi-carbide B4C-SiC/(Al, Si) composites were produced by the reactive melt infiltration technique at 1200 – 1350 °C with up to 1 hour of isothermal temperature holds. Pressed preforms made from C-containing B4C were spontaneously infiltrated with Al-Si alloys of composition varying from 25 to 50 wt% Si. The present study involves the characterisation of the microstructure and crystalline phases in the alloys and in the composites by X-ray diffraction and SEM/EDS with EBSD. Electron backscatter diffraction is used in detail to look for segregation and spatial distribution of Si and Al containing phases during solidification of the metallic infiltrate inside the channels of the ceramic matrix when the composite cools down to the eutectic temperature (577 °C). It complements elemental maps of the SEM/EDS. The production of a flat surface by polishing is intrinsically difficult and the problems inherent to the preparation of EBSD qualified finishing in polished samples of such type of composites are further discussed

  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)

    Steel matrix composites locally reinforced with different molar ratios of in situ TiC/TiB2 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-B4C and Ni-Ti-B4C-C systems during casting. Differential thermal analysis (DTA) and X-ray diffraction (XRD) results reveal that the exothermic reactions of the Ni-Ti-B4C and Ni-Ti-B4C-C systems proceed in such a way that Ni initially reacts with B4C and Ti to form Ni2B and Ti2Ni 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 TiB2 at 1133 deg. C. In the composites reinforced with 1:2 molar ratio of TiC/TiB2, almost all TiB2 grains have clubbed structures, while TiC grains exhibit near-spherical morphologies. Furthermore, TiB2 grain sizes decrease, with the increase of TiC content. In particular, in the composites reinforced with 2:1 molar ratio of TiC/TiB2, it is difficult to find the clubbed TiB2 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/TiB2, while a few macro-pores can be observed in the composite reinforced with 2:1 molar ratio of TiC/TiB2. Moreover, the densities of the composites reinforced with 1:1 and 1:2 molar ratios of TiC/TiB2 are higher than that of the composite reinforced with 2:1 molar ratio of TiC/TiB2. The composite reinforced with 1:2 molar ratio of TiC/TiB2 has the highest hardness and the best wear resistance

  15. Degradation in steam of 60 cm-long B4C control rods

    Science.gov (United States)

    Dominguez, C.; Drouan, D.

    2014-08-01

    In the framework of nuclear reactor core meltdown accident studies, the degradation of boron carbide control rod segments exposed to argon/steam atmospheres was investigated up to about 2000 °C in IRSN laboratories. The sequence of the phenomena involved in the degradation has been found to take place as expected. Nevertheless, the ZrO2 oxide layer formed on the outer surface of the guide tube was very protective, significantly delaying and limiting the guide tube failure and therefore the boron carbide pellet oxidation. Contrary to what was expected, the presence of the control rod decreases the hydrogen release instead of increasing it by additional oxidation of boron compounds. Boron contents up to 20 wt.% were measured in metallic mixtures formed during degradation. It was observed that these metallic melts are able to attack the surrounding fuel rods, which could have consequences on fuel degradation and fission product release kinetics during severe accidents.

  16. 10B4C Multi-Grid as an alternative to 3He for Large Area Neutron Detectors

    OpenAIRE

    Correa Magdalena, Jonathan

    2012-01-01

    Despite its present shortage, 3He continues to be the most common neutron converter for detectors in neutron scattering science. However, it is obvious that the development of large area neutron detectors based on alternative neutron converters is rapidly becoming a matter of urgency. In the technique presented, grids each comprising 30 10B4C layers (each 1 µm thick) are used to convert neutrons into ionising particles which are subsequently detected in proportional gas counters. Several pro...

  17. 10B4C Multi-Grid as an alternative to 3He for Large Area Neutron Detectors

    OpenAIRE

    Correa Magdalena, Jonathan; Guerard, Bruno; Campo Ruiz, Jesús Javier

    2013-01-01

    Despite its present shortage, 3He continues to be the most common neutron converter for detectors in neutron scattering science. However, it is obvious that the development of large area neutron detectors based on alternative neutron converters is rapidly becoming a matter of urgency. In the technique presented, grids each comprising 30 10B4C layers (each 1 µm thick) are used to convert neutrons into ionising particles which are subsequently detected in proportional gas counters. Several pro...

  18. High temperature tribological behaviour of carbon based (B4C and DLC) coatings in sliding contact with aluminum

    International Nuclear Information System (INIS)

    Carbon based coatings, particularly diamond-like carbon (DLC) films are known to resist aluminum adhesion and reduce friction at room temperature. This attractive tribological behaviour is useful for applications such as tool coatings used for aluminum forming and machining. However, for those operations that are performed at elevated temperatures (e.g. hot forming) or that generate frictional heat during contact (e.g. dry machining) the suitable coatings are required to maintain their tribological properties at high temperatures. Candidates for these demanding applications include boron carbide (B4C) and DLC coatings. An understanding of the mechanisms of friction, wear and adhesion of carbon based coatings against aluminum alloys at high temperatures will help in designing coatings with improved high temperature tribological properties. With this goal in mind, this study focused on B4C and a hydrogenated DLC coatings sliding against a 319 grade cast aluminum alloy by performing pin-on-disk experiments at temperatures up to 400 oC. Experimental results have shown that the 319 Al/B4C tribosystem generated coefficient of friction (COF) values ranging between 0.42 and 0.65, in this temperature range. However, increased amounts of aluminum adhesion were detected in the B4C wear tracks at elevated temperatures. Focused ion beam (FIB) milled cross sections of the wear tracks revealed that the coating failed due to shearing along the columnar grain boundaries of the coating. The 319 Al/DLC tribosystem maintained a low COF (0.15-0.06) from room temperature up to 200 oC. This was followed by an abrupt increase to 0.6 at 400 oC. The deterioration of friction behaviour at T > 200 oC was attributed to the exhaustion of hydrogen and hydroxyl passivants on the carbon transfer layer formed on the Al pin.

  19. Effects of B4C addition on the micro- structural and thermal properties of hot pressed SiC ceramic matrix composites

    OpenAIRE

    Z. Keçeli; H. Ögünç; T. Boyraz; H. Gökçe; O. Addemir; M. Lütfi Öveçoğlu

    2009-01-01

    Purpose: The purpose of paper is to evaluate effects of B4C addition on the microstructural and thermal properties of hot pressed SiC ceramic matrix composites.Design/methodology/approach: The effect of B4C addition on microstructural and thermal properties of the SiC-B4C powder composites were investigated after high energy milling and hot pressing. SiC powders containing 5wt%, 10wt%, 15wt% B4C were mechanically alloyed in a high energy ball mill for 8 h.Findings: Microstructural characteris...

  20. Electronic transport in boron carbides: temperature (4K-300K), frequency (0-1 GHz) and composition (B13C2-B4C) effects

    International Nuclear Information System (INIS)

    Boron carbide is a light ceramics of industrial interest. The equilibrium diagram reveals a large compositional range (B9C to B4C). The compositions close to the boundary B4C are obtained by pressing directly in graphite dies while the other compositions were obtained by using boron nitride lined graphite dies and boron additions to the commercial powders. The starting point of the present study was the idea to use the electrical transport properties as possible ways of characterising the industrial materials. We were thus led to measure at low temperatures dc and ac conductivity, dielectric constant and thermopower. The successful study of a measurement method for ac measurements between 10 KHz and 1 GHz and between 4 K and 300 K was one of the main experimental points of the present work. ac measurements have permitted a clear separation between bulk and grain boundary effects on the transport. The bulk results were analysed in terms of the usual conduction models in disordered solids (hopping, polarons...)

  1. Development and Characterization of B4C Reinforced Detonation-Sprayed Al Coatings

    Science.gov (United States)

    Tillmann, W.; Hollingsworth, P. S.; Fischer, G.; Nellesen, J.; Beckmann, F.

    2014-02-01

    Because of their excellent properties aluminum and its alloys cover a wide range of applications especially in the lightweight construction sector. In order to reach a higher strength and wear resistance metal matrix composites (MMCs) are used. Typically Al MMCs are manufactured by casting or extrusion processes. The disadvantage of these production routes is a cost-intensive and time-consuming finishing in terms of grinding and milling. The technique of thermal spraying provides the possibility to coat aluminum parts with MMCs close to their final shape. In addition to the shape accuracy the ductility and toughness of the coated parts are generally higher compared to extruded or casted parts. This study describes the development of detonation-sprayed boron carbide reinforced aluminum coatings on aluminum (EN AW 5754) substrates. The optimization of the coatings was focused on a homogeneous coating structure, a low coating porosity, a high deposition efficiency, a high number of embedded carbides, and a small percentage of oxides. In continuous tensile tests the influence of the MMC coating on the tensile strength was determined. Furthermore, the tensile strength was investigated in a discontinuous tensile test step by step. The different stages of deformation were analyzed by using micro computed tomography. This method enables the observation of tensile specimens in 3D, and consequently the site and moment of crack formation.

  2. Deposition and characterization of B4C/CeO2 multilayers at 6.x nm extreme ultraviolet wavelengths

    Science.gov (United States)

    Sertsu, M. G.; Giglia, A.; Brose, S.; Park, D.; Wang, Z. S.; Mayer, J.; Juschkin, L.; Nicolosi, P.

    2016-03-01

    New multilayers of boron carbide/cerium dioxide (B4C/CeO2) combination on silicon (Si) substrate are manufactured to represent reflective-optics candidates for future lithography at 6.x nm wavelength. This is one of only a few attempts to make multilayers of this kind. Combination of several innovative experiments enables detailed study of optical properties, structural properties, and interface profiles of the multilayers in order to open up a room for further optimization of the manufacturing process. The interface profile is visualized by high-angle annular dark-field imaging which provides highly sensitive contrast to atomic number. Synchrotron based at-wavelength extreme ultraviolet (EUV) reflectance measurements near the boron (B) absorption edge allow derivation of optical parameters with high sensitivity to local atom interactions. X-ray reflectivity measurements at Cu-Kalpha (8 keV ) determine the period of multilayers with high in-depth resolution. By combining these measurements and choosing robust nonlinear curve fitting algorithms, accuracy of the results has been significantly improved. It also enables a comprehensive characterization of multilayers. Interface diffusion is determined to be a major cause for the low reflectivity performance. Optical constants of B4C and CeO2 layers are derived in EUV wavelengths. Besides, optical properties and asymmetric thicknesses of inter-diffusion layers (interlayers) in EUV wavelengths near the boron edge are determined. Finally, ideal reflectivity of the B4C/CeO2 combination is calculated by using optical constants derived from the proposed measurements in order to evaluate the potentiality of the design.

  3. Atomic structure of icosahedral B4C boron carbide from a first principles analysis of NMR spectra.

    Science.gov (United States)

    Mauri, F; Vast, N; Pickard, C J

    2001-08-20

    Density functional theory is demonstrated to reproduce the 13C and 11B NMR chemical shifts of icosahedral boron carbides with sufficient accuracy to extract previously unresolved structural information from experimental NMR spectra. B4C can be viewed as an arrangement of 3-atom linear chains and 12-atom icosahedra. According to our results, all the chains have a CBC structure. Most of the icosahedra have a B11C structure with the C atom placed in a polar site, and a few percent have a B (12) structure or a B10C2 structure with the two C atoms placed in two antipodal polar sites.

  4. A W:B4C multilayer phase retarder for broadband polarization analysis of soft x-ray radiation

    OpenAIRE

    MacDonald, Michael A.; Schaefers, Franz; Pohl, R.; Poole, Ian B.; Gaupp, Andreas; Quinn, Frances M.

    2008-01-01

    A W:B4C multilayer phase retarder has been designed and characterized which shows a nearly constant phase retardance between 640 and 850 eV photon energies when operated near the Bragg condition. This freestanding transmission multilayer was used successfully to determine, for the first time, the full polarization vector at soft x-ray energies above 600 eV, which was not possible before due to the lack of suitable optical elements. Thus, quantitative polarimetry is now possible at the 2p edge...

  5. Fabrication of Al5083/B4C surface composite by friction stir processing and its tribological characterization

    Directory of Open Access Journals (Sweden)

    Narayana Yuvaraj

    2015-10-01

    Full Text Available Improved surface properties with the retainment of bulk properties are necessary for a component for enhanced wear characteristics. Friction stir processing (FSP is used to produce such surface composites. Fabrication of 5083 aluminum alloy with reinforced layers of boron carbide (B4C through FSP was carried out. Micro and nano sized B4C particles were used as reinforcements. The friction processed surface composite layer was analyzed through optical and scanning electron microscopical studies. The number of passes and the size of reinforcement play a vital role in the development of surface composites by FSP. Mechanical properties of the friction stir processed surface composites were evaluated through micro hardness and universal tensile tests. The results were compared with the properties of the base metal. The role of reinforcement and number of passes on properties were also evaluated. Tribological performance of the surface composites is tested through pin on disk test. The surface composite layer resulted in three passes with nano particle reinforcement exhibited better properties in hardness, tensile behavior and wear resistance compared to the behavior of the base metal.

  6. Thermal and stress studies of normal incidence Mo/B4C multilayers for a 6.7 nm wavelength.

    Science.gov (United States)

    Barthelmess, Miriam; Bajt, Saša

    2011-04-10

    Wavelength, reflectance, and stress stability of Mo/B(4)C multilayers were studied as a function of postdeposition annealing up to 900 °C. These multilayers are of interest as normal incidence coatings for wavelengths above the boron K-absorption edge. Mo/B(4)C multilayers deposited at low sputtering pressure have high compressive stress. Zero stress can be achieved at 360 °C-370 °C, but annealing at boron carbide layers separated by amorphous layers of molybdenum borides (Mo(x)B(y)) is presented. These interlayers are present already in the as-deposited state and continue to grow with increasing temperature. Their presence lowers the optical contrast and the achievable reflectivity. However, they also increase multilayer thermal stability. At temperatures >600 °C, a noticeable decrease in reflectivity associated with the phase transition from amorphous to crystalline molybdenum boride is observed. This is accompanied with an increase in interface and surface roughness and a change in stress as a function of temperature.

  7. Laser controlled melting of H12 hot-work tool steel with B4C particles at the surface

    Science.gov (United States)

    Yilbas, B. S.; Patel, F.; Karatas, C.

    2015-11-01

    Laser controlled melting of pre-prepared H12 hot-work tool steel surface is carried out. B4C particles in the carbon film are located at the workpiece surface prior to the laser treatment process. Nitrogen at high pressure is used as an assisting gas during the laser melting. Morphological and metallurgical changes in the treated layer are examined using scanning electron microscope, energy dispersive spectroscopy, and X-ray diffraction. Microhardness of the treated surface is measured and the residual stress formed at the treated surface vicinity is obtained using the X-ray diffraction technique. It is found that a dense layer consisting of fine grains is formed at the treated surface. Microhardness of the treated surface improves significantly because of fine grains, nitride compounds formed at the surface and micro-stresses developed due to mismatched of thermal expansion coefficients of B4C and the base material. The residual stress formed at the surface is suppressed by the self annealing effect of the initially formed laser scans.

  8. Neutron reflectometry on highly absorbing films and its application to 10B4C-based neutron detectors

    Science.gov (United States)

    Piscitelli, F.; Khaplanov, A.; Devishvili, A.; Schmidt, S.; Höglund, C.; Birch, J.; Dennison, A. J. C.; Gutfreund, P.; Hall-Wilton, R.; Van Esch, P.

    2016-01-01

    Neutron reflectometry is a powerful tool used for studies of surfaces and interfaces. The absorption in the typical studied materials is neglected and this technique is limited only to the reflectivity measurement. For strongly absorbing nuclei, the absorption can be directly measured by using the neutron-induced fluorescence technique which exploits the prompt particle emission of absorbing isotopes. This technique is emerging from soft matter and biology where highly absorbing nuclei, in very small quantities, are used as a label for buried layers. Nowadays, the importance of absorbing layers is rapidly increasing, partially because of their application in neutron detection; a field that has become more active also due to the 3He-shortage. We extend the neutron-induced fluorescence technique to the study of layers of highly absorbing materials, in particular 10B4C. The theory of neutron reflectometry is a commonly studied topic; however, when a strong absorption is present the subtle relationship between the reflection and the absorption of neutrons is not widely known. The theory for a general stack of absorbing layers has been developed and compared to measurements. We also report on the requirements that a 10B4C layer must fulfil in order to be employed as a converter in neutron detection. PMID:26997902

  9. High frequency complex permeability of flake-shaped Fe74Cr2Mo2Sn2P10Si4B4C2 particle composite material

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A composite consisting of flake-shaped Fe74Cr2Mo2Sn2P10Si4B4C2 particles was prepared.The flake-shaped particles included in the composite were prepared by planetary ball milling.The complex permeability of the composite material was measured at frequency range from 10 MHz to 8.5 GHz.The permeability of the composite containing flake-shaped particles was much higher than that of the spherical particles.The permeability of particles was improved by means of heat-treatment.In contrast to the random-spatial-distributed flake-shaped particle composites,the oriented-distributed ones had a higher effective permeability.A model was proposed considering the orientation ratio,and our calculation agreed well with the experimental data.

  10. Effect of the content of B4C on microstructural evolution and wear behaviors of the laser-clad coatings fabricated on Ti6Al4V

    Science.gov (United States)

    Bai, L. L.; Li, J.; Chen, J. L.; Song, R.; Shao, J. Z.; Qu, C. C.

    2016-01-01

    TiNi/Ti2Ni-based composite coatings reinforced by TiC and TiB2 were produced on Ti6Al4V by laser cladding the mixture of a Ni-based alloy and different contents of B4C (0 wt%, 5 wt%, 15 wt%, and 25 wt%). The macromorphologies and microstructures of the coatings were examined through optical microscopy, X-ray diffractometry, scanning electron microscopy, and energy dispersive spectrometry. The microhardness, fracture toughness, and wear behaviors of the coatings were also investigated by using a microhardness tester and an ultra-functional wear testing machine. Results showed that the coatings were mainly composed of TiNi/Ti2Ni and TiC/TiB2 as the matrix and reinforcement particles, respectively. The phase constituents of the coatings were not influenced by addition of different contents of B4C. The microstructure of the reinforcements in the coatings presented the following evolution: hypereutectic consisting of blocky (TiC+TiB2)e eutectic and primary TiCp cellular dendrites (0 wt% B4C), mixture of hypereutectic and willow-shaped (TiB2+TiC)p pseudoeutectic (5 wt% B4C), and pseudoeutectic (15 and 25 wt% B4C). With increasing B4C content, the volume fraction and size of the pseudoeutectic structures as well as the average microhardness of the coatings (850, 889, 969, and 1002 HV0.2) were increased. By contrast, the average fracture toughness of the coatings was gradually decreased (4.47, 4.21, 4.06, and 3.85 Mpa m1/2) along with their wear volumes (0 wt%, 5 wt%, and 15 wt% B4C). The increase in B4C content to 25 wt% did not further reduce wear loss. The wear mechanism transformed from micro-cutting (0 wt% B4C) into a combination of micro-cutting and brittle debonding (5 wt% B4C) and finally led to brittle debonding (15 wt% and 25 wt% B4C). Coatings with suitable contents of B4C (less than 15 wt%) showed excellent comprehensive mechanical properties.

  11. Investigation on the Behaviours of TiB2 Reinforced B4C-SiC Composites Against Co-60 Gamma Radioisotope Source

    OpenAIRE

    Bülent Büyük; Tuğrul, Beril A.

    2015-01-01

    In the present study, the gamma attenuation behaviours of the Titanium diboride (TiB2) reinforced boron carbide (B4C)-silicon carbide (SiC) composite materials were investigated against Co-60 gamma radioisotope source. In the experiments TiB2 unreinforced and 2% and 4% TiB2 (by volume) reinforced B4C-SiC composite materials were used. In the composite materials B4C/SiC ratio has been realized as 6/4 by volume. The linear and mass attenuation coefficients of the samples were carried out for Co...

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

    International Nuclear Information System (INIS)

    Burnable poison rods, made of B4C- Al2 O3 pellets with 5.01 mg/cm310 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)

  13. Preparation and Its Properties of Vanadium Carbide Coating Through B4C Reducing V2O5

    Institute of Scientific and Technical Information of China (English)

    WangBiao; WangYudong; ZhangZihua

    2005-01-01

    A vanadium carbide coating on steel's substrates was prepared through B4C reducing V2O5 in molten salt bath. The thickness of VC-coating reached 14-18μm at 920℃ for 6h, and the hardness of VC-coating reached HV2200-HV2400. The sliding wear resistance of the VC-coating is not only 3350 times of that of SCN-coating, but also more excellent than that of other VC-coatings, prepared through aluminum reducing V2O5 or through TD processing. The experimental results indicate that the different VC-coating resistances to wear and corrosion increase with a raise of the free carbon contents in VC-coatings. The continuous service life of a tongue grooves of the high speed cigarette machines, with this VC-coating, reached good results of 140-150days.

  14. Simulation response of B4C-coated PPAC for thermal neutrons using GEANT4 Monte Carlo approach

    Science.gov (United States)

    Jamil, M.; Rhee, J. T.; Jeon, Y. J.

    2013-08-01

    In this work we report a technique employed for the detection of thermal neutrons using the parallel plate avalanche counter (PPAC). In order to make the detector sensitive to thermal neutrons a thin layer of B4C has been coated on the forward electrode of the PPAC configuration. Upon falling on the converter coating, charged particles were generated via the 10B (n , α)7Li reaction. In this simulation study, thermal neutrons have been simulated using the GEANT4 MC code, and the response of the detector has been evaluated as a function of neutron energy. For a better understanding of the simulation response, the performance of the detector has been found using the two different physics list i.e., QGSP _ BIC _ HP and QGSP _ BERT _ HP. The obtained results predict that such boron-carbide based PPAC can be potentially utilized for thermal neutron detection. A complete description of the detector configuration and the simulation results is also presented.

  15. Fabrication and characterization of hybrid structured Al alloy matrix composites reinforced by high volume fraction of B4C particles

    International Nuclear Information System (INIS)

    In the present paper, hybrid structured B4C particles reinforced Al2024 matrix composites were prepared by the powder metallurgy method. The composites made from 100% mechanical milled composite powders have fracture strength of 670 MPa. With the addition of un-milled Al2024 powder increased from 10 vol% to 40 vol%, the room temperature compression strength decreased from 1115 MPa to 739 MPa, without any visible plastic deformation. However, when the fraction of un-milled Al2024 powder increased to 50 vol%, the compression strength was decreased to 580 MPa, while retaining a remarkable fracture strain up to 10%. The microstructures of the composites with different composition were examined by a scanning electron microscope and a transmission electron microscope. The contribution from different strengthening mechanisms was discussed. The hybrid structures are proved to account for the dramatic change of the fracture mechanism of the composites

  16. Synthesis of B4C-Nano TiB2 Composite Powder by Sol-Gel Method

    Science.gov (United States)

    Baharvandi, H. R.; Talebzadeh, N.; Ehsani, N.; Aghand, F.

    2009-04-01

    Production of (B4C-nano TiB2) composite powder by chemical method was evaluated in this study. Starting materials were boron carbide, carbon, and titanium (IV) iso propoxide (TTIP). Water was used as a hydrolyser agent. TTIP was hydrolyzed with water and, consequently, amorphous Ti(OH)4 was formed. Heat-treatment of Ti(OH)4 at 100 and 850 °C led to the production of TiO2 and TiB2 phases, respectively. The effect of heat-treatment time and temperature on the phase transformation and size of the produced nano powder were investigated. The produced nano powder was characterized by XRD, SEM, and DTA. It was found that heat-treatment time and temperature have significant effects on the amount and size of the produced TiB2 powder. The data also reveal that the minimum temperature for TiB2 formation is 650 °C.

  17. Influence of B4C to TTIP Molar Ratio on Synthesis of Nano Titanium Diboride Powders via Sol-Gel Method

    Science.gov (United States)

    Sinaei Pour Fard, Hamed; Baharvandi, Hamidreza; Abdizadeh, Hossein

    Titanium diboride (TiB2) has attracted great interests for its excellent mechanical properties, chemical resistance and good thermal and electrical conductivities. So it is widely applied as cutting tool composites, wear resistant parts, metal melting crucibles and electrode materials. This paper presents synthesis of nano titanium diboride powders via sol-gel method using a mixture of TTIP and B4C as precursors. In the hydrolysis step, B4C to TTIP molar ratio varied from 1.3 to 2.5. Solution samples stirred well and after aging and drying process, they were heat treated in an argon atmosphere. X-ray diffraction (XRD) patterns and Scanning electron microscopy (SEM) analysis showed that the percentage of synthesized TiB2 increased gradually as the molar ratio of B4C to TTIP reached to 2.3, afterward increasing the B4C to TTIP molar ratio caused decreasing of titanium diboride percentage.

  18. Effects of B4C addition on the micro- structural and thermal properties of hot pressed SiC ceramic matrix composites

    Directory of Open Access Journals (Sweden)

    Z. Keçeli

    2009-12-01

    Full Text Available Purpose: The purpose of paper is to evaluate effects of B4C addition on the microstructural and thermal properties of hot pressed SiC ceramic matrix composites.Design/methodology/approach: The effect of B4C addition on microstructural and thermal properties of the SiC-B4C powder composites were investigated after high energy milling and hot pressing. SiC powders containing 5wt%, 10wt%, 15wt% B4C were mechanically alloyed in a high energy ball mill for 8 h.Findings: Microstructural characterisation investigations (SEM, XRD were carried out on mechanically alloyed SiC powder composites containing 5 wt %, 10 wt %, 15 wt % B4C powders and on these powder composites sintered in vacuum at 50 MPa at 2100ºC. The thermal properties were characterised using DTA, TGA and dilatometer. The results were evaluated.Research limitations/implications: In this study, the effect of B4C addition on microstructural and mechanical properties of the SiC-B4C powder composites was investigated after high energy milling and hot pressing.Originality/value: Ceramic matrix composite (CMC material systems are stimulating a lot of interest to be used and provide unique properties for aircraft and land-based turbine engines, defence applications, rocket motors, aerospace hot structures and industrial applications. Boron carbide (B4C-silicon carbide (SiC ceramic composites are very promising armour materials because they are intrinsically very hard. Advanced SiC-based armour is desired so that the projectile is completely defeated without penetrating the ceramic armour.

  19. Pseudo- in-situ stir casting: a new method for production of aluminum matrix composites with bimodal-sized B4C reinforcement

    Science.gov (United States)

    Raei, Mohammad; Panjepour, Masoud; Meratian, Mahmood

    2016-08-01

    A new method was applied to produce an Al-0.5wt%Ti-0.3wt%Zr/5vol%B4C composite via stir casting with the aim of characterizing the microstructure of the resulting composite. For the production of the composite, large B4C particles (larger than 75 μm) with no pre-heating were added to the stirred melt. Reflected-light microscopy, X-ray diffraction, scanning electron microscopy, field-emission scanning electron microscopy, laser particle size analysis, and image analysis using the Clemex software were performed on the cast samples for microstructural analysis and phase detection. The results revealed that as a consequence of thermal shock, B4C particle breakage occurred in the melt. The mechanism proposed for this phenomenon is that the exerted thermal shock in combination with the low thermal shock resistance of B4C and large size of the added B4C particles were the three key parameters responsible for B4C particle breakage. This breakage introduced small particles with sizes less than 10 μm and with no contamination on their surfaces into the melt. The mean particle distance measured via image analysis was approximately 60 μm. The coefficient of variation index, which was used as a measure of particle distribution homogeneity, showed some variations, indicating a relatively homogeneous distribution.

  20. Photocatalytic CO2 reduction over B4C/C3N4 with internal electric field under visible light irradiation.

    Science.gov (United States)

    Zhang, Xiaojie; Wang, Lei; Du, Quanchao; Wang, Zhiyong; Ma, Shuguo; Yu, Miao

    2016-02-15

    Boron carbide/graphitic carbon nitride (B4C/g-C3N4) p-n hetero-junction photocatalyst with an internal electric field was synthesized by a facile solvent evaporation method and characterized by field emission scanning electron microscope (FESEM), UV-Vis diffuse reflectance spectra (UV-Vis DRS), photoluminescence spectra (PL), etc. Photocatalytic activity of the composite B4C/g-C3N4 loaded with Pt co-catalyst was evaluated using CO2 conversion to CH4 with H2 as the hydrogen source and reductant under visible light irradiation. The coupling of p-type B4C with n-type g-C3N4 significantly improved the performance of photocatalytic CO2 reduction; with the optimum B4C mass fraction of 1/6, the composite photocatalyst showed approximately 6 and 8 times higher CH4 generation rate than g-C3N4 and B4C, respectively. The enhancement was attributed to efficient photo-excited electron/hole separation due to the formation of internal electric field at the p-B4C/n-C3N4 interface.

  1. Chemical compatibility of B4C/Na/S.S.. Pt.1: The effects of temperature and B/C ratio

    International Nuclear Information System (INIS)

    B4C pellets with different B/C ratio and nuclear purity grade sodium were put into a stainless steel cladding tubes and the out-of-pile tests were carried out at 550, 650 and 750 degree C. The test period is 82 d. After compatibility test, the appearance of B4C pellets is integral, and crack or break are not found. However, the surfaces become rough and original metal luster is lost. The chemical reaction product NaB5O8 deposits and adheres to the surface of B4C pellets. This results in the volume increasing of B4C pellets. No considerable change in microstructure and grain size of B4C pellets are observed. There are B, Na and C penetrate into cladding inner surface. The amount of B and Na penetration increases with the temperature and B/C ratio increasing, but C penetration is opposite. The chemical reaction products among Na, impurities in sodium, B4C and cladding are NaBO2 , Cr2B, Fe2B and Ni3B. The formation of the borides made increasing considerably in microhardness at the cladding inner surface

  2. High Heat Flux Testing of B4C/Cu and SiC/Cu Functionally Graded Materials Simulated by Laser and Electron Beam

    Institute of Scientific and Technical Information of China (English)

    刘翔; 谌继明; 张斧; 许增裕; 葛昌纯; 李江涛

    2002-01-01

    B4C, SiC and C, Cu functionally graded-materials (FGMs) have been developed by plasma spraying and hot pressing. Their high-heat flux properties have been investigated by high energy laser and electron beam for the simulation of plasma disruption process of the future fusion reactors, And a study on eroded products of B4C/Cu FGM under transient thermal load of electron beam was performed. In the experiment, SEM and EDS analysis indicated that B4C and SiC were decomposed, carbon was preferentially evaporated under high thermal load, and a part of Si and Cu were melted, in addition, the splash of melted metal and the particle emission of brittle destruction were also found. Different erosive behaviors of carbon-based materials (CBMs) caused by laser and electron beam were also discussed.

  3. The Effect of Calcination Temperature on Synthesis of B4C-Nano Tib2 Composite by Co-Precipitation Method

    Directory of Open Access Journals (Sweden)

    Saeid Abedini Khorrami

    2016-08-01

    Full Text Available Titanium diboride is one of the candidate materials for high temperature applications and also for control rod elements in high temperature reactors. This paper presents the experimental data on the composites of B4C-nano TiB2 that were synthesized successfully by co-precipitation method at temperatures between 973 and 1523K. Titanium tetraisopropoxide, boron carbide and isopropanol were used as the precursor materials. The phase constitution and microstructure of B4C-nano TiB2 during synthesis were investigated. X-ray diffraction (XRD and scanning electron microscopy (SEM were used to determine phase and microstructure of TiB2-B4C composites. The DTA/DDTA and TG/DTG results improve that the first exothermic reaction is TiO2 phase and second exothermic reaction takes place at 1523K which is TiB2 phase

  4. High heat flux testing of B4C/Cu and SiC/Cu functionally graded materials simulated by laser and electron beam

    International Nuclear Information System (INIS)

    B4C, SiC and C, Cu functionally graded-materials (FGMs) have been developed by plasma spraying and hot pressing. Their high-heat flux properties have been investigated by high energy laser and electron beam for the simulation of plasma disruption process of the future fusion reactors. And a study on eroded products of B4C/Cu FGM under transient thermal load of electron beam was performed. In the experiment, SEM and EDS analysis indicated that B4C and SiC were decomposed, carbon was preferentially evaporated under high thermal load, and a part of Si and Cu were melted, in addition, the splash of melted metal and the particle emission of brittle destruction were also found. Different erosive behaviors of carbon-based materials (CBMs) caused by laser and electron beam were also discussed

  5. 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.

  6. Investigation on the Behaviours of TiB2 Reinforced B4C-SiC Composites Against Co-60 Gamma Radioisotope Source

    Directory of Open Access Journals (Sweden)

    Bülent Büyük

    2015-02-01

    Full Text Available In the present study, the gamma attenuation behaviours of the Titanium diboride (TiB2 reinforced boron carbide (B4C-silicon carbide (SiC composite materials were investigated against Co-60 gamma radioisotope source. In the experiments TiB2 unreinforced and 2% and 4% TiB2 (by volume reinforced B4C-SiC composite materials were used. In the composite materials B4C/SiC ratio has been realized as 6/4 by volume. The linear and mass attenuation coefficients of the samples were carried out for Co60 gamma radioisotope source which has two energy peaks (1.17 and 1.33 MeV. Then mass attenuation coefficients and half-value thicknesses (HVT of the materials were calculated. Experimental mass attenuation coefficients were compared with the theoretical values which were calculated from XCOM computer code. Furthermore HVTs of the samples were evaluated and compared each other. It has been seen that the experimental and theoretical mass attenuation coefficients are closed to each other and differences are under 10 percent. In addition, TiB2 reinforced B4C-SiC composites have smaller HVTs than unreinforced one. Moreover 4% TiB2 reinforced B4C-SiC composite has smaller HVT than the 2% reinforced sample. Reinforcing TiB2 and increasing TiB2 ratio increase the gamma attenuation property of the B4C-SiC composites against Co-60 gamma radioisotope source.

  7. Low pressure hot pressing of B4C matrix ceramic composites improved by Al2O3 and TiC additives

    International Nuclear Information System (INIS)

    B4C matrix ceramic composites toughened by Al2O3 and TiC were prepared by low pressure hot pressing. The relative density, Vickers hardness, fracture toughness and flexural strength of the new fabricated composites were measured. Microstructure observations of the fracture surfaces and the indentation cracks of the B4C matrix ceramic composites were analyzed, and an X-ray diffraction phase analysis was performed. The experiment results showed that chemical reactions took place during the low pressure hot pressing process and resulted in the B4C/Al2O3/TiB2 composite. The densification rate of the B4C matrix ceramic composites was enhanced and the mechanical properties were improved via the introduction of Al2O3 and TiC additives. The Vickers hardness, fracture toughness and flexural strength of the composite with the addition of 4.7 wt.% Al2O3 and 10 wt.% TiC were 24.8 GPa, 4.8 MPa m1/2 and 445 MPa, respectively.

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

    International Nuclear Information System (INIS)

    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%B4C 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%B4C 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 B4C particles and acceptable cohesion between B4C and matrix.

  9. Preparation for B4C/Mo2C multilayer deposition of alternate multilayer gratings with high efficiency in the 0.5-2.5 keV energy range

    Science.gov (United States)

    Choueikani, Fadi; Delmotte, Franck; Bridou, Françoise; Lagarde, Bruno; Mercere, Pascal; Otero, Edwige; Ohresser, Philippe; Polack, François

    2013-03-01

    This paper presents a study of B4C/Mo2C multilayers mirrors with the aim of using it in the achievement of Alternate MultiLayer (AML) grating. Such component allows a high efficiency in the 500-2500 eV energy range for the DEIMOS beamline. Multilayers were deposited on silicon substrate. They are characterized by reflectometry under grazing incidence. Numerical adjustments were performed with a model of two layers in the period without any interfacial. A prototype of AML grating was fabricated and characterized. The efficiency of the first order of diffraction was worth 15% at 1700 eV.

  10. A Comparative Study on SiC-B4C-Si Cermet Prepared by Pressureless Sintering and Spark Plasma Sintering Methods

    Science.gov (United States)

    Sahani, P.; Karak, S. K.; Mishra, B.; Chakravarty, D.; Chaira, D.

    2016-06-01

    Silicon carbide (SiC)-boron carbide (B4C) based cermets were doped with 5, 10, and 20 wt pct Silicon (Si) and their sinterability and properties were investigated for conventional sintering at 2223 K (1950 °C) and spark plasma sintering (SPS) at 1623 K (1350 °C). An average particle size of ~3 µm was obtained after 10 hours of milling. There is an enhancement of Vickers microhardness in the 10 wt pct Si sample from 18.10 in conventional sintering to 27.80 GPa for SPS. The relative density, microhardness, and indentation fracture toughness of the composition SiC60(B4C)30Si10 fabricated by SPS are 98 pct, 27.80 GPa, and 3.8 MPa m1/2, respectively. The novelty of the present study is to tailor the wettability and ductility of the cermet by addition of Si into the SiC-B4C matrix. Better densification with improved properties is achieved for cermets consolidated by SPS at lower temperatures than conventional sintering.

  11. Development of electroless Ni-P-B4C composite coatings%镍-磷-碳化硼化学复合镀层的研制

    Institute of Scientific and Technical Information of China (English)

    KARTHIKEYAN S; VENKATACHALAM G; SRINIVASAN K N; VASUDEVAN T; NARAYANAN S

    2011-01-01

    Ni-P-B4C composite coatings were prepared on mild steel by electroless plating from a stable bath containing nickel carbonate 15 g/L, hypophosphorous acid 32 mL/L, sodium hypophosphite 15 g/L, lactic acid 32 mL/L, acetic acid 18 g/L, propionic acid 3 mL/L, dimethylamine 1.7 g/L, and boron carbide (B4C) particles 0-25 g/L. The microhardness of the composite coatings was examined by Vickers tester, the wear resistance by Taber abrasion tester, the microscopic morphology and structure by SEM and X-ray diffraction, and the corrosion resistance by potenfiodynamic polarization and electrochemical impedance spectroscopy. The incorporation of B4C increases the microhardness, wear resistance, and corrosion resistance of the Ni-P alloy matrix. The Ni-P-B4C composite coating features a popcorn-like structure with coarse-grained composite particles.%在由碳酸镍15 g/L、次磷酸32 mL/L、次磷酸钠15 g/L、乳酸32mL/L、乙酸189/L、丙酸3mL/L、二甲胺1.7g/L及碳化硼(即B4C)0~25 g/L组成的稳定镀液中,采用化学镀的方法在低碳钢上制备了Ni-P-B4C复合镀层.其显微硬度采用韦氏硬度法测量,耐磨性用Taber磨耗试验机测量,微观形貌和组织采用扫描电镜和X射线衍射进行分析,耐蚀性以动电位极化及电化学阻抗谱测定.碳化硼的掺入提高了镍-磷合金基体的显微硬度、耐磨性和耐蚀性.Ni-P-B4C复合镀层颗粒粗大,具有爆米花式组织结构.

  12. Carbon-rich icosahedral boron carbides beyond B4C and their thermodynamic stabilities at high temperature and pressure from first principles

    Science.gov (United States)

    Ektarawong, A.; Simak, S. I.; Alling, B.

    2016-08-01

    We investigate the thermodynamic stability of carbon-rich icosahedral boron carbide at different compositions, ranging from B4C to B2C , using first-principles calculations. Apart from B4C , generally addressed in the literature, B2.5C , represented by B10C2p (C-C), where Cp and (C-C) denote a carbon atom occupying the polar site of the icosahedral cluster and a diatomic carbon chain, respectively, is predicted to be thermodynamically stable under high pressures with respect to B4C as well as pure boron and carbon phases. The thermodynamic stability of B2.5C is determined by the Gibbs free energy G as a function of pressure p and temperature T , in which the contributions from the lattice vibrations and the configurational disorder are obtained within the quasiharmonic and the mean-field approximations, respectively. The stability range of B2.5C is then illustrated through the p -T phase diagrams. Depending on the temperatures, the stability range of B2.5C is predicted to be within the range between 40 and 67 GPa. At T ≳ 500 K, the icosahedral Cp atoms in B2.5C configurationally disorder at the polar sites. By investigating the properties of B2.5C , e.g., elastic constants and phonon and electronic density of states, we demonstrate that B2.5C is both mechanically and dynamically stable at zero pressure, and is an electrical semiconductor. Furthermore, based on the sketched phase diagrams, a possible route for experimental synthesis of B2.5C as well as a fingerprint for its characterization from the simulations of x-ray powder diffraction pattern are suggested.

  13. Determination of gamma ray attenuation coefficients of Al–4% Cu/B4C metal matrix composites at 662, 1173 and 1332 keV

    Indian Academy of Sciences (India)

    I Akkurt; K Günoğlu; A Çalik; M S Karakas

    2014-08-01

    Gamma ray attenuation coefficients of metal matrix composites have been investigated. For this purpose, the linear attenuation coefficients of composites containing boron carbide (B4C) at different rates have been measured using a gamma spectrometer that contains a NaI(Tl) detector and MCA at 662, 1173 and 1332 keV, which are obtained from 137Cs and 60Co sources. The measured results were compared with the calculation obtained using computer code of XCOM for 1 keV–1 GeV gamma energies.

  14. Effect of particle size and percentages of Boron carbide on the thermal neutron radiation shielding properties of HDPE/B4C composite: Experimental and simulation studies

    Science.gov (United States)

    Soltani, Zahra; Beigzadeh, Amirmohammad; Ziaie, Farhood; Asadi, Eskandar

    2016-10-01

    In this paper the effects of particle size and weight percentage of the reinforcement phase on the absorption ability of thermal neutron by HDPE/B4C composites were investigated by means of Monte-Carlo simulation method using MCNP code and experimental studies. The composite samples were prepared using the HDPE filled with different weight percentages of Boron carbide powder in the form of micro and nano particles. Micro and nano composite were prepared under the similar mixing and moulding processes. The samples were subjected to thermal neutron radiation. Neutron shielding efficiency in terms of the neutron transmission fractions of the composite samples were investigated and compared with simulation results. According to the simulation results, the particle size of the radiation shielding material has an important role on the shielding efficiency. By decreasing the particle size of shielding material in each weight percentages of the reinforcement phase, better radiation shielding properties were obtained. It seems that, decreasing the particle size and homogeneous distribution of nano forms of B4C particles, cause to increase the collision probability between the incident thermal neutron and the shielding material which consequently improve the radiation shielding properties. So, this result, propose the feasibility of nano composite as shielding material to have a high performance shielding characteristic, low weight and low thick shielding along with economical benefit.

  15. Hot Extrusion Process Effect on Mechanical Behavior of Stir Cast Al Based Composites Reinforced with Mechanically Milled B4C Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    A. Alizadeh1; E. Taheri-Nassaj; M. Hajizamani

    2011-01-01

    In this study, aluminum alloy (Al-2 wt% Cu) matrix composites reinforced with 1, 2 and 4 wt% boron carbide nanoparticles fabricated through mechanical milling with average size of 100 nm were fabricated via stir casting method at 850℃. Cast ingots of the matrix alloy and the composites were extruded at 500℃ at an extrusion ratio of 10:1 to investigate the effects of hot extrusion on the mechanical properties of the composites. The microstructures of the as-cast and the extruded composites were investigated by scanning electron microscopy (SEM). Density measurement, hardness and tensile tests were carried out to identify the mechanical properties of the composites. The extruded samples revealed a more uniform distribution of B4C nanoparticles. Also, the extruded samples had strength and ductility values superior to those of the as-cast counterparts. In the as-cast and the extruded samples, with increasing amount of B4C nanoparticles, yield strength and tensile strength increased but elongation to fracture decreased.

  16. Hybridizing micro-Ti with nano-B4C particulates to improve the microstructural and mechanical characteristics of Mg–Ti composite

    Directory of Open Access Journals (Sweden)

    S. Sankaranarayanan

    2014-03-01

    Full Text Available In this study, the effects of hybridizing micron-sized titanium particles with nano-sized boron carbide particles on the microstructural and mechanical properties of Mg–Ti composite were investigated. Microstructural characterization revealed grain refinement attributed to the presence of uniformly distributed micro-Ti particles embedded with nano-B4C particulates. Electron back scattered diffraction (EBSD analyses of the Mg–(Ti + B4CBM hybrid composite showed relatively more localized recrystallized grains and lesser tensile twin fraction, when compared to Mg–Ti. The evaluation of mechanical properties indicated that the best combination of strength and ductility was observed in the Mg–(Ti + B4CBM hybrid composite. The superior properties of the Mg–(Ti + B4CBM hybrid composite when compared to Mg–Ti can be attributed to the presence of nano-reinforcement, the uniform distribution of the hybridized particles and the better interfacial bonding between the matrix and the reinforcement particles achieved by nano-B4C addition.

  17. Chemical compatibility of B-4C/Na/S.S. system. Pt.2: Effects of test period and oxygen content in sodium

    International Nuclear Information System (INIS)

    The simulation specimens of the fast breeder reactor' control rod were put into the thermal convection sodium loop, and the out of pile tests for B4C/Na/S.S. system chemical compatibility were performed at 550 degree C, and the effects of the test period and oxygen content in sodium on the compatibility characters were investigated. The appearance of B4C pellets is integral, and crack or break are not found after compatible test. There is B penetration in cladding inner surface, the amount of B penetration is proportional to the square root of the test period. The depth of B penetration is not changed with the add of the test period. The microhardness at the cladding inner surface increases clearly, its increment is increasing slightly with the add of the test period. The depth of the hardening layers is about 40 μm for different test periods. The reaction products Cr2B, Na4B10O17, B6Fe23, CrB, Nib and NiB12 are formed according to priority at the cladding inner surface for 80 to 400 d. The diffusion of B into the cladding relates to the temperature, test period and the oxygen content, and the oxygen promotes the B diffusion

  18. Proton-induced nanorod melting in a coating obtained from the pulsed laser ablation of W2B5/B4C

    International Nuclear Information System (INIS)

    Highlights: • Coatings from ablated B4C/W2B5 were irradiated with 900 keV protons. • Nanorod clusters were observed to melt and disperse. • Uniformly shaped nanorods were observed to grow. • Lateral diffusion of energy and lateral dispersion of matter were observed. - Abstract: Coatings obtained from pulsed laser ablated W2B5/B4C were irradiated with 900keV protons at fluences ranging from about 1×1015protons/cm2 to about 4×1015protons/cm2. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) were used to study the resulting structural effects. Clusters of nanorods were observed to disperse and reduce in number with increase in proton fluence. The atomic percentage of constituent elements were observed to vary with proton fluence, both within the nanorods and the film floor. Our results show that the structural effect of proton irradiation on the coating is lateral dispersion of matter

  19. Electrical Discharge Machining of Al (6351-5% SiC-10% B4C Hybrid Composite: A Grey Relational Approach

    Directory of Open Access Journals (Sweden)

    S. Suresh Kumar

    2014-01-01

    Full Text Available The goal of the present experimental work is to optimize the electrical discharge machining (EDM parameters of aluminum alloy (Al 6351 matrix reinforced with 5 wt.% silicon carbide (SiC and 10 wt.% boron carbide (B4C particles fabricated through the stir casting route. Multiresponse optimization was carried out through grey relational analysis (GRA with an objective to minimize the machining characteristics, namely electrode wear ratio (EWR, surface roughness (SR and power consumption (PC. The optimal combination of input parameters is identified, which shows the significant enhancement in process characteristics. Contributions of each machining parameter to the responses are calculated using analysis of variance (ANOVA. The result shows that the pulse current contributes more (83.94% to affecting the combined output responses.

  20. Microstructure and Crystallographic Texture Variations in the Friction-Stir-Welded Al-Al2O3-B4C Metal Matrix Composite Produced by Accumulative Roll Bonding

    Science.gov (United States)

    Mohammadnezhad, Mahyar; Shamanian, Morteza; Zabolian, Azam; Taheri, Mahshid; Javaheri, Vahid; Navidpour, Amir Hossein; Nezakat, Majid; Szpunar, Jerzy A.

    2015-12-01

    In this research, ultrafine-grained sheets of aluminum matrix composite (Al-Al2O3-B4C) were produced by accumulative roll bonding ARB technique. As-received, ultrafine-grained aluminum composite sheets were joined by friction-stir welding. The microstructure, crystallographic texture, and Vickers hardness in the weld zones were investigated. Electron backscattered diffraction results revealed occurrence of dynamic recrystallization and demonstrated existence of different grain orientations within the weld nugget. Produced composite plates illustrated rotated cubic texture. Moreover, in the nugget, a well-recrystallized grain structure having characteristic strong shear texture component finally developed. However, the texture result in the heat-affected zone illustrated rotated cubic and Goss components that related to the effect of heat input. Friction-stir welding refined the grain size in the weld zone. The hardness also improved with the peak hardness being observed towards the advancing stir welding side.

  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)

    Burnable poison rods made of Al2O3-B4C pellets with different concentrations of 10B 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 10B 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/cm3 of 10B. 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

    Energy Technology Data Exchange (ETDEWEB)

    Dhir, S.; Uppaluri, R. [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam (India); Purkait, M.K. [Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam (India)], E-mail: mihir@iitg.ernet.in

    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{sub 2}O{sub 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.

    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. PMID:18541367

  4. Effects of configurational disorder on the elastic properties of icosahedral boron-rich alloys based on B6O, B13C2, and B4C, and their mixing thermodynamics

    Science.gov (United States)

    Ektarawong, A.; Simak, S. I.; Hultman, L.; Birch, J.; Tasnádi, F.; Wang, F.; Alling, B.

    2016-04-01

    The elastic properties of alloys between boron suboxide (B6O) and boron carbide (B13C2), denoted by (B6O)1-x(B13C2)x, as well as boron carbide with variable carbon content, ranging from B13C2 to B4C are calculated from first-principles. Furthermore, the mixing thermodynamics of (B6O)1-x(B13C2)x is studied. A superatom-special quasirandom structure approach is used for modeling different atomic configurations, in which effects of configurational disorder between the carbide and suboxide structural units, as well as between boron and carbon atoms within the units, are taken into account. Elastic properties calculations demonstrate that configurational disorder in B13C2, where a part of the C atoms in the CBC chains substitute for B atoms in the B12 icosahedra, drastically increase the Young's and shear modulus, as compared to an atomically ordered state, B12(CBC). These calculated elastic moduli of the disordered state are in excellent agreement with experiments. Configurational disorder between boron and carbon can also explain the experimentally observed almost constant elastic moduli of boron carbide as the carbon content is changed from B4C to B13C2. The elastic moduli of the (B6O)1-x(B13C2)x system are also practically unchanged with composition if boron-carbon disorder is taken into account. By investigating the mixing thermodynamics of the alloys, in which the Gibbs free energy is determined within the mean-field approximation for the configurational entropy, we outline the pseudo-binary phase diagram of (B6O)1-x(B13C2)x. The phase diagram reveals the existence of a miscibility gap at all temperatures up to the melting point. Also, the coexistence of B6O-rich as well as ordered or disordered B13C2-rich domains in the material prepared through equilibrium routes is predicted.

  5. 激光熔覆B4C-TiO2-Al粉末制备原位TiB2+TiC/Fe复合涂层%Production of in situ TiB2+TiC/Fe composite coating from precursor containing B4C-TiO2-Al powders by laser cladding

    Institute of Scientific and Technical Information of China (English)

    王新洪; 潘向宁; 杜宝帅; 李帅

    2013-01-01

    Steel matrix composites reinforced with TiB2+TiC reinforcement were produced by laser melting mixture of B4C, TiO2, Al and Fe-based self-melting alloy powders. The results show that TiB2+TiC ceramic particles were synthesized from the reaction of B4C, TiO2 and Al alloys during laser cladding process. The reinforcement particles were evenly distributed in the coating. TiB2 grew in rectangle shape, but TiC presented irregular cubic shape. The wear resistance of the coating was higher than that of the substrate of 1045 steel;meanwhile, the friction coefficient of the coating was considerably lower than that of 1045 steel.%采用 B4C、 TiO2、Al 以及 Fe 基自熔合金粉末为前驱体,利用激光熔覆技术在钢基体上制备 TiB2+TiC颗粒增强Fe基复合涂层。结果表明,激光熔覆过程通过B4C−TiO2−Al反应生成了均匀分布于基体的TiB2−TiC复合陶瓷相。TiB2颗粒呈长条块状,TiC以不规则形状分布于基体中。涂层具有比基材1045钢更好的耐磨性能,但涂层的摩擦因数小。

  6. 以聚碳硅烷包覆B4C为原料温压-烧结原位制备SiC/B4C复相陶瓷%SiC/B4C Multiphase Ceramics Using Polycarbosilane-Coating B4C as Raw Materials Prepared In-suit by Warm Pressing and Sintering

    Institute of Scientific and Technical Information of China (English)

    林文松; 何亮

    2011-01-01

    B4 C/SiC pellets were prepared by warm pressing of polycarbosilane-coating boron carbide powder at the temperature of 300 ℃ under the pressure of 50 Mpa, and cold isostatic pressing under the pressure of 800 Mpa, respectively. The samples were then kept warm at 1 200 ℃ for 2 h in flowing Ar, with subsequent sintering for 3 h between 1 800 and 2 000 ℃ in vacuum. Relative densities, phases and microstructures of the multiphase ceramics were investigated. The results show that the multiphase ceramics prepared by warm pressing (WP) had higher density than that by cold isostatic pressing (CIP). The multiphase ceramics with maximum relative density was achieved after the warm pressing green bodies containing 15% SiC sintered for 3 h, and its relative density was more than 93%. The multiphase ceramics consisted of B4C and SiC and SiC phases distributed uniformly on the B1C particles interface.%以聚碳硅烷(PCS)包覆B4C粉为原料,分别在300℃、50 MPa下温压成型和800MPa下冷等静压成型,而后将压坯置于氩气气氛保护下在1 200℃保温2 h,再在1 800~2 000℃下真空烧结3 h,原位反应制备出SiC/B4C复相陶瓷;研究了它的相对密度、物相组成和显微结构。结果表明:温压工艺比冷等静压工艺能得到更高密度的复相陶瓷;合15%SoC的温压压坯在烧结3 h后得到复相陶瓷的相对密度大于93%;复相陶瓷由B4C和SiC相组成,SiC相均匀分布在B4C颗粒界面上。

  7. Chemical Compatibility of B4C/Na/S.S.Ⅰ.The Effects of Temperature and B/C Ratio%B4C/Na/S.S.三元体系的化学相容性Ⅰ.温度效应及B/C比的影响

    Institute of Scientific and Technical Information of China (English)

    许咏丽; 龙斌; 张道德

    2000-01-01

    在堆用不锈钢包壳管内分别填装不同B/C比的B4C芯块及核级钠,以模拟快堆控制棒内的B4C/Na/S.S.三元体系,在堆外550、650和750 ℃下相互作用82 d.试验后的B4C芯块外观完整,未见掉角、龟裂或破碎;表面变得粗糙,失去原有的金属光泽,化学反应产物NaB5O8等在表面沉积和粘附,并导致B4C芯块体积增大;芯块的微观结构和晶粒度试验前后无明显变化.包壳管内表面渗B、渗Na和渗C,渗B和渗Na量均随温度升高和B/C比增大而增加,渗C则反之.Na和Na中杂质以及B4C与包壳间的化学反应产物为NaBO2、Cr2B、Fe2B和Ni3B.B化物的形成使包壳管内表面显微硬度显著增大.

  8. Wet oxidation of a spacecraft model waste

    Science.gov (United States)

    Johnson, C. C.; Wydeven, T.

    1985-01-01

    Wet oxidation was used to oxidize a spacecraft model waste under different oxidation conditions. The variables studied were pressure, temperature, duration of oxidation, and the use of one homogeneous and three heterogeneous catalysts. Emphasis is placed on the final oxidation state of carbon and nitrogen since these are the two major components of the spacecraft model waste and two important plant nutrients.

  9. 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)

    The fabrication of medium carbon steel-matrix composites locally reinforced with in situ TiB2-TiC particulates using self-propagating high-temperature synthesis (SHS) reaction of Ni-Ti-B4C 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-B4C system. As-cast microstructures of the in situ processed composites reveal a relatively uniform distribution of TiB2-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 TiB2 and TiC particulates can be fabricated. Although most of fine TiB2 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-B4C systems are higher than those of the composites synthesized from 10 to 20 wt.% Ni-Ti-B4C systems

  10. Chemical Compatibility of B4C/Na/S.S. System Ⅱ. Effects of Test Period and Oxygen Content in Sodium%B4C/Na/S.S.三元体系化学相容性研究Ⅱ.相容时间及钠中氧含量的影响

    Institute of Scientific and Technical Information of China (English)

    许咏丽; 龙斌; 张道德

    2000-01-01

    将快堆控制棒模拟样品置于高温热对流钠回路中,于550 ℃下进行B4C/Na/S.S.三元体系化学相容性试验,研究相容时间及钠中氧含量对相互作用特性的影响.结果表明:试验后的B4C芯块完整,无掉角、龟裂或破碎;包壳管内表面渗B,渗B量与相容时间的平方根成正比,渗B深度不随相容时间变化;包壳管内表面显微硬度明显升高,其升高幅度随相容时间增长略有增大,不同相容时间下的硬化层深度均约为40 μm;相容时间从80 d增加到400 d,包壳管内表面相继出现反应产物Cr2B,Na4B10O17,B6Fe23,CrB和NiB,NiB12;B向包壳管内表面的扩散与温度、相容时间及钠中氧含量有关,氧对B的扩散起促进作用.

  11. B4C颗粒增强铝基复合材料微观形貌和力学行为分析%Microstructure and Mechanical Behavior of B4C-Aluminium Composite

    Institute of Scientific and Technical Information of China (English)

    高占平; 王文先; 李宇力; 王保东

    2012-01-01

    通过中温热压法(热压温度在固液相线之间)制备出不同碳化硼含量的铝基复合材料,并轧制成板.经T6热处理后对B4C/Al复合材料进行微观形貌、力学性能分析.结果表明,碳化硼颗粒分布均匀,有较少的微气孔缺陷,随着碳化硼含量的增加,增强颗粒尺寸明显变小.B4C/Al复合材料的抗拉强度、屈服强度和断后伸长率随着碳化硼含量的增加而减小,与6061铝合金相比降低幅度较大,硬度随着碳化硼含量的增加而提高,靠近颗粒处硬度显著提高.B4C/Al复合材料的断裂方式是脆性断裂.%By medium-temperature hot pressing method (hot-pressing temperature between the solid and liquid phase line), the boron carbide aluminum matrix composite with different B4C content was successfully prepared, and was rolled into boards. After T6 heatment, the microstructure and mechanical behavior of the composite were analyzed. The results show that the distribution of boron carbide particle is uniform, and there are few micro-hole defects in the composite. Along with the increase of the content of boron carbide, the grain size significantly decreases, the tensile strength, yield strength and percentage elongation after fracture of B4C/A1 composite reduces along with the increase of the content of boron carbide, which is less than that of 6061 Al alloy. The hardness of the composite increases with the increase of boron carbide. Especially, the hardness closing to the grain significantly enhances. The fracture mechanism of the composite is brittle fracture.

  12. Creep behavior in interlaminar shear of a Hi-NicalonTM/ SiC-B4C composite at 1200∘C in air and in steam

    Directory of Open Access Journals (Sweden)

    Ruggles-Wrenn Marina

    2015-01-01

    Full Text Available 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-NicalonTM 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.

  13. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  14. Al-B4C复合材料在硼酸溶液中腐蚀机理研究%Corrosion Mechanism of Al-B4C Composite Materials in Boric Acid

    Institute of Scientific and Technical Information of China (English)

    石建敏; 沈春雷; 张玲; 雷家荣; 龙兴贵; 周晓松

    2012-01-01

    采用硼酸溶液模拟乏燃料贮存水池环境,研究A1-B4C复合材料在其中的腐蚀行为.用SEM、EDS观测腐蚀试样的微观形貌,用XRD测试腐蚀前后试样的物相,并测试腐蚀过程中试样的干重.结果表明:材料中的Al是引起腐蚀的主要因素;0~500 ppm硼酸溶液中,试样腐蚀增重,在表面生成斜晶结构的Al(OH)3氧化膜,对材料起一定保护作用;2500 ppm硼酸溶液中,试样腐蚀增重,在表面沉积非晶结构的Al(OH)3絮状腐蚀产物;10 000~25000 ppm硼酸溶液中,试样腐蚀失重,表面局部微小区域可观察到龟裂和腐蚀“坑”生成.材料抗腐蚀性能随溶液硼酸浓度的增加而降低,欲提高材料抗腐蚀性能,需对其进行表面保护处理.%A boric acid solution was used to simulate the environment of actual spent fuel storage. The corrosion behaviors of A1-B4C composite materials in boric acid solutions were investigated. The microscopic morphology was observed by SEM and EDS. The phases of samples before and after the corrosion tests were measured by XRD and the dry weight of the samples was also measured. The results show that the corrosion is caused by aluminum in the A1-B4C composite; a dense layer of A1(OH)3 is formed after corrosion test in boric acid solution at 0 to 500 ppm and the samples gain weight after corrosion test; an amorphous A1(OH)3 sediments with wadding structure are found after corrosion in boric acid solution at 2 500 ppm and the samples also gain weight; some local areas appeared chapped and the corroded pits can be observed after corrosion in boric solution at 10 000 to 25 000 ppm and the samples lost weight. The corrosion resistance decreases with the increasing of concentration of boric acid. In order to improve the corrosion resistance, it is necessary to make a surface protection on A1-B4C composite.

  15. COSP - A computer model of cyclic oxidation

    Science.gov (United States)

    Lowell, Carl E.; Barrett, Charles A.; Palmer, Raymond W.; Auping, Judith V.; Probst, Hubert B.

    1991-01-01

    A computer model useful in predicting the cyclic oxidation behavior of alloys is presented. The model considers the oxygen uptake due to scale formation during the heating cycle and the loss of oxide due to spalling during the cooling cycle. The balance between scale formation and scale loss is modeled and used to predict weight change and metal loss kinetics. A simple uniform spalling model is compared to a more complex random spall site model. In nearly all cases, the simpler uniform spall model gave predictions as accurate as the more complex model. The model has been applied to several nickel-base alloys which, depending upon composition, form Al2O3 or Cr2O3 during oxidation. The model has been validated by several experimental approaches. Versions of the model that run on a personal computer are available.

  16. Thermal Safety Analysis of Aluminum Matrix B4C In-Pile Irradiation%铝基碳化硼堆内辐照热工安全分析

    Institute of Scientific and Technical Information of China (English)

    米向秒; 钱达志; 邓勇军; 张之华; 黄洪文; 郭海兵

    2012-01-01

    Aluminum matrix B4C is a new structural material for spent fuel storage and related performances need in-depth research, especially the irradiation resistance capability. The thermal calculations were completed by using the CFD software to ensure the safety of the in-pile irradiation test. Considering the characteristic of the irradiation project, the thermal safety feature of the in-pile test was analyzed, and the irradiation project was optimized.q%铝基碳化硼是一种新型的乏燃料贮存架结构材料,需对其各项性能进行研究,其中,铝基碳化硼材料的耐辐照性能是关键参数之一.为进行铝基碳化硼材料的堆内辐照考验,并保证其在堆内辐照的安全,针对铝基碳化硼辐照方案的特点,采用了CFD程序进行热工校核计算,分析了铝基碳化硼材料在堆内辐照的安全特性,优化了堆内辐照方案.

  17. 铝基碳化硼材料堆内辐照方案设计%Design of Aluminum Matrix B4C In-Core Irradiation Test Program

    Institute of Scientific and Technical Information of China (English)

    袁姝; 冯琦杰; 郭海兵; 刘晓; 邓勇军

    2012-01-01

    铝基碳化硼是一种新型的乏燃料贮存格架用材料,为检验其辐照性能,需进行堆内辐照实验.本文从样品成分及形状、辐照罐结构、辐照位置等方面,对铝基碳化硼材料堆内辐照方案进行设计.经初步中子物理学和热工计算表明:在所选择的两个辐照孔道内进行辐照考验,试件所接受的累积γ射线照射剂量和相应的快中子积分注量均满足技术要求,且辐照罐样品入堆后对功率峰值因子、反应性、发热率等与堆运行安全相关因子的影响均在安全范围内.%As a new candidate for spent fuel storage framework material, in-core irradiation test for aluminum matrix boron carbide (B4C) was performed to evaluate its irradiation behavior. The experiment was designed and analyzed according to sample's composition and shape, irradiation box characters, and core arrangement. The neutronic and thermal hydraulic simulations indicate that the scheme of the experiment chosen can meet the requirement of all parameters, such as y dose, integral fast neutron flux, power peaking factor, core reactivity, and sample heating rate.

  18. Modeling selective intergranular oxidation of binary alloys

    Science.gov (United States)

    Xu, Zhijie; Li, Dongsheng; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

    2015-01-01

    Intergranular attack of alloys under hydrothermal conditions is a complex problem that depends on metal and oxygen transport kinetics via solid-state and channel-like pathways to an advancing oxidation front. Experiments reveal very different rates of intergranular attack and minor element depletion distances ahead of the oxidation front for nickel-based binary alloys depending on the minor element. For example, a significant Cr depletion up to 9 μm ahead of grain boundary crack tips was documented for Ni-5Cr binary alloy, in contrast to relatively moderate Al depletion for Ni-5Al (˜100 s of nm). We present a mathematical kinetics model that adapts Wagner's model for thick film growth to intergranular attack of binary alloys. The transport coefficients of elements O, Ni, Cr, and Al in bulk alloys and along grain boundaries were estimated from the literature. For planar surface oxidation, a critical concentration of the minor element can be determined from the model where the oxide of minor element becomes dominant over the major element. This generic model for simple grain boundary oxidation can predict oxidation penetration velocities and minor element depletion distances ahead of the advancing front that are comparable to experimental data. The significant distance of depletion of Cr in Ni-5Cr in contrast to the localized Al depletion in Ni-5Al can be explained by the model due to the combination of the relatively faster diffusion of Cr along the grain boundary and slower diffusion in bulk grains, relative to Al.

  19. Modelling of UO2 oxidation in steam

    International Nuclear Information System (INIS)

    A computer model has been developed for calculating oxidation of UO2 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)

  20. Nonequilibrium Thermodynamic Model of Manganese Carbonate Oxidation

    Institute of Scientific and Technical Information of China (English)

    郝瑞霞; 彭省临

    1999-01-01

    Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.

  1. Application of Substitutional Model in Oxide Systems

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The application of substitutional model in oxide systems, in comparison with that of sublattice model, is discussed.The results show that in the case of crystalline phases and liquid phases without molecular-like associates or theshortage of element in sublattice, these two models get consistent in the description of the formalism of Gibbs freeenergies of phases and obtain the same result of phase diagram calculation when the valence of the cations keep thesame.

  2. An analysis of the impact of native oxide, surface contamination and material density on total electron yield in the absence of surface charging effects

    Science.gov (United States)

    Iida, Susumu; Ohya, Kaoru; Hirano, Ryoichi; Watanabe, Hidehiro

    2016-10-01

    The effects of the presence of a native oxide film or surface contamination as well as variations in material density on the total electron yield (TEY) of Ru and B4C were assessed in the absence of any surface charging effect. The experimental results were analyzed using semi-empirical Monte Carlo simulations and demonstrated that a native oxide film increased the TEY, and that this effect varied with film thickness. These phenomena were explained based on the effect of the backscattered electrons (BSEs) at the interface between Ru and RuO2, as well as the lower potential barrier of RuO2. Deviations in the material density from the theoretical values were attributed to the film deposition procedure based on fitting simulated TEY curves to experimental results. In the case of B4C, the TEY was enhanced by the presence of a 0.8-nm-thick surface contamination film consisting of oxygenated hydrocarbons. The effect of the low potential barrier of the contamination film was found to be significant, as the density of the B4C was much lower than that of the Ru. Comparing the simulation parameters generated in the present work with Joy's database, it was found that the model and the input parameters used in the simulations were sufficiently accurate.

  3. Role of friction stir welding parameters on tensile strength ofAA6061-B4C composite joints%搅拌摩擦焊接工艺参数对AA6061-B4C焊接接头抗拉强度的影响

    Institute of Scientific and Technical Information of China (English)

    K.KALAISELVAN; N.MURUGAN

    2013-01-01

    搅拌摩擦焊(FSW)是一种固态连接技术,可用来连接高强度铝合金及多种陶瓷颗粒增强金属基复合材料(MMCs).搅拌摩擦焊获得的陶瓷增强金属基复合材料焊缝优良,在增强体与基体间没有发生有害反应.对搅拌摩擦焊接工艺参数对AA6061-B4C焊接接头抗拉强度的影响进行研究.采用4因素5水平的中心复合设计来控制实验的次数.构建一数学模型来分析搅拌摩擦焊工艺参数对接头抗拉强度的影响.结果表明,在旋转速度1000r/min、焊接速度1.3 mm/s、轴向力10kN、增强相含量12%的条件下,搅拌摩擦焊得到的焊接接头的抗拉强度最大.根据构建的模型采用广义简约梯度算法进行优化以得到最大的抗拉强度.金相分析表明,在焊接接头中出现了多种区域,如焊合区、热力影响区和热影响区.在焊合区观察到大量的被细化的铝基体晶粒以及粒径明显减小的B4C颗粒.在热力影响区出现塑性变形、热影响和被拉长的铝晶粒.%Friction stir welding (FSW) is a solid state joining technique developed to join high strength aluminum alloys and various ceramic reinforced metal matrix composites (MMCs).FSW produces sound welds in MMCs without any deleterious reaction between reinforcement and matrix.The present work focused on the effect of FSW parameters on the tensile strength of Al-B4C composite joints.The central composite design of four factors and five levels was used to control the number of experiments.A mathematical model was developed to analyze the influence of FSW parameters.The results indicated that the joint fabricated using rotational speed of 1000 r/min,welding speed of 1.3 mm/s,axial force of 10 kN and the reinforcement of 12% showed larger tensile strength compared with the other joints.The developed model was optimized to maximize the tensile strength using generalized reduced gradient method.The metallographic analysis of the joints showed the presence

  4. A Self-Consistent Model for Thermal Oxidation of Silicon at Low Oxide Thickness

    OpenAIRE

    Gerlach, Gerald; Maser, Karl

    2016-01-01

    Thermal oxidation of silicon belongs to the most decisive steps in microelectronic fabrication because it allows creating electrically insulating areas which enclose electrically conductive devices and device areas, respectively. Deal and Grove developed the first model (DG-model) for the thermal oxidation of silicon describing the oxide thickness versus oxidation time relationship with very good agreement for oxide thicknesses of more than 23 nm. Their approach named as general relationship ...

  5. Modelling the oxidation of defected fuel elements

    International Nuclear Information System (INIS)

    Interim dry storage of used fuel is an economical alternative to storage in water pools. The fuel must remain intact during the dry-storage period, otherwise future handling of the fuel will be expensive. Oxidation of defected fuel elements can lead to fuel disintegration. Thus it is important to be able to predict the extent of oxidation of defected fuel elements in a dry-storage facility. In this report, a model is developed for predicting the extent or rate of oxidation of defected fuel elements stored at temperatures up to 170 C. The model employs equivalent porous medium representation of the fuel and described the oxygen concentration in the fuel element using a reaction-diffusion equation. The one- and two-dimensional reaction-diffusion equations are solved on the assumption that the oxygen-fuel reaction is either zeroth or first order in the oxygen concentration. Dimensional analysis of the model equations shows that the solution depends explicitly on a single parameter p. The value of p can be calculated using data from the literature, or it can be estimated from the results of the CEX-1 experiments being carried out at Whiteshell Laboratories. The value of p, estimated from the CEX-1 results, is more than two orders of magnitude larger than the value of p calculated from literature data. Although some reasons for this large difference are suggested, further work is needed to resolve this discrepancy. (author). 16 refs., 2 tabs., 11 figs

  6. Research Progress in Boron Carbide-Aluminum Composites with Applications to Storage and Transportation of Reactor Spent Fuel%用于反应堆乏燃料贮存和运输的B4C/Al复合材料研究进展

    Institute of Scientific and Technical Information of China (English)

    鲜亚疆; 庞晓轩; 王伟; 刘鹏闯; 张鹏程

    2015-01-01

    B4C/Al复合材料是一种集结构和功能于一体的中子吸收材料,在反应堆乏燃料贮存和运输领域有着广阔的应用前景.综述了B4C/Al复合材料的主要制备工艺及国内外研究现状,并展望了未来的发展方向,最后指出随着我国核电事业的发展,B4C颗粒增强铝基复合材料将作为研究重点并在辐射屏蔽领域广泛应用.

  7. A Self-Consistent Model for Thermal Oxidation of Silicon at Low Oxide Thickness

    Directory of Open Access Journals (Sweden)

    Gerald Gerlach

    2016-01-01

    Full Text Available Thermal oxidation of silicon belongs to the most decisive steps in microelectronic fabrication because it allows creating electrically insulating areas which enclose electrically conductive devices and device areas, respectively. Deal and Grove developed the first model (DG-model for the thermal oxidation of silicon describing the oxide thickness versus oxidation time relationship with very good agreement for oxide thicknesses of more than 23 nm. Their approach named as general relationship is the basis of many similar investigations. However, measurement results show that the DG-model does not apply to very thin oxides in the range of a few nm. Additionally, it is inherently not self-consistent. The aim of this paper is to develop a self-consistent model that is based on the continuity equation instead of Fick’s law as the DG-model is. As literature data show, the relationship between silicon oxide thickness and oxidation time is governed—down to oxide thicknesses of just a few nm—by a power-of-time law. Given by the time-independent surface concentration of oxidants at the oxide surface, Fickian diffusion seems to be neglectable for oxidant migration. The oxidant flux has been revealed to be carried by non-Fickian flux processes depending on sites being able to lodge dopants (oxidants, the so-called DOCC-sites, as well as on the dopant jump rate.

  8. 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.

  9. Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation

    Science.gov (United States)

    Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert

    2008-08-01

    The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.

  10. 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.

  11. Multiscale model of metal alloy oxidation at grain boundaries

    International Nuclear Information System (INIS)

    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 Cr2O3. 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 NiAl2O4. 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. Cr2O3 has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl2O4 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 pathway for

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

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, G G [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 (Cu{sub 2}O), 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 > Cu{sub 2}O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu{sub 2}O, 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 N{sub 2} and CO{sub 2}. At the end of each reaction, the catalyst was found to be Cu{sub 2}O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  13. Extension of silicon emission model to silicon pillar oxidation

    Science.gov (United States)

    Kageshima, Hiroyuki; Shiraishi, Kenji; Endoh, Tetsuo

    2016-08-01

    Missing Si in the oxidation of Si pillar structures is investigated by extending the Si emission model to the oxidation of planar structures. The original Si emission model [H. Kageshima et al., Jpn. J. Appl. Phys. 38, L971 (1999)] assumes the emission of excess Si from the interface into the oxide during the oxidation process, the diffusion of the excess Si through the oxide, and the control of the oxidation rate by the concentration of remaining excess Si around the interface. By assuming the sublimation of the excess Si from the oxide surface in addition to the assumptions of the original Si emission model, the origin of the missing Si is consistently explained. It is suggested that the amount of the missing Si is enhanced by the geometrical effect of the pillar structure because the concentration of excess Si is inversely proportional to the radial position. This also suggests that the missing Si is inevitable for the thin pillar structures. Careful approaches to the oxidation process are recommended for pillar structures.

  14. 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.

  15. A cladding oxidation model based on diffusion equations

    International Nuclear Information System (INIS)

    During severe accident in PWRs, the cladding oxidation with steam in the core is very important to the accident process. When oxidation time is long, or oxidation occurs in steam starvation conditions, the parabolic rate correlations based on experiments are restricted, which impacts the prediction of cladding failure, hydrogen production, and temperature. According to Fick's laws, a cladding oxidation model in a wide temperature range based on diffusion equations is developed. The developed oxidation model has a wider applicability than those parabolic rate correlations, and can simulate long-term experiments well. The restricted assumptions of short term oxidation time and enough steam environment in the core implemented by those parabolic rate correlations are removed in the model, therefore this model perfectly fit for long-term and steam starvation conditions which are more realistic during a severe accident. This model also can obtain detailed oxygen distribution in the cladding, which is helpful to simulate the cladding failure in detail and develop advanced cladding failure criteria. (authors)

  16. 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

  17. Modeling oxidation damage of continuous fiber reinforced ceramic matrix composites

    Institute of Scientific and Technical Information of China (English)

    Cheng-Peng Yang; Gui-Qiong Jiao; Bo Wang

    2011-01-01

    For fiber reinforced ceramic matrix composites (CMCs), oxidation of the constituents is a very important damage type for high temperature applications. During the oxidizing process, the pyrolytic carbon interphase gradually recesses from the crack site in the axial direction of the fiber into the interior of the material. Carbon fiber usually presents notch-like or local neck-shrink oxidation phenomenon, causing strength degradation. But, the reason for SiC fiber degradation is the flaw growth mechanism on its surface. A micromechanical model based on the above mechanisms was established to simulate the mechanical properties of CMCs after high temperature oxidation. The statistic and shearlag theory were applied and the calculation expressions for retained tensile modulus and strength were deduced, respectively. Meanwhile, the interphase recession and fiber strength degradation were considered. And then, the model was validated by application to a C/SiC composite.

  18. Modeling of oxidation of aluminum nanoparticles by using Cabrera Mott Model

    Science.gov (United States)

    Ramazanova, Zamart; Zyskin, Maxim; Martirosyan, Karen

    2012-10-01

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

  19. Modelling nitrous oxide emissions from organic soils in Europe

    Science.gov (United States)

    Leppelt, Thomas; Dechow, Rene; Gebbert, Sören; Freibauer, Annette

    2013-04-01

    The greenhouse gas emission potential of peatland ecosystems are mandatory for a complete annual emission budget in Europe. The GHG-Europe project aims to improve the modelling capabilities for greenhouse gases, e.g., nitrous oxide. The heterogeneous and event driven fluxes of nitrous oxide are challenging to model on European scale, especially regarding the upscaling purpose and certain parameter estimations. Due to these challenges adequate techniques are needed to create a robust empirical model. Therefore a literature study of nitrous oxide fluxes from organic soils has been carried out. This database contains flux data from boreal and temperate climate zones and covers the different land use categories: cropland, grassland, forest, natural and peat extraction sites. Especially managed crop- and grassland sites feature high emission potential. Generally nitrous oxide emissions increases significantly with deep drainage and intensive application of nitrogen fertilisation. Whereas natural peatland sites with a near surface groundwater table can act as nitrous oxide sink. An empirical fuzzy logic model has been applied to predict annual nitrous oxide emissions from organic soils. The calibration results in two separate models with best model performances for bogs and fens, respectively. The derived parameter combinations of these models contain mean groundwater table, nitrogen fertilisation, annual precipitation, air temperature, carbon content and pH value. Influences of the calibrated parameters on nitrous oxide fluxes are verified by several studies in literature. The extrapolation potential has been tested by an implemented cross validation. Furthermore the parameter ranges of the calibrated models are compared to occurring values on European scale. This avoid unknown systematic errors for the regionalisation purpose. Additionally a sensitivity analysis specify the model behaviour for each alternating parameter. The upscaling process for European peatland

  20. 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.

  1. 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.

  2. Kinetic modeling of oxidative desulfurization and catalyst deactivation

    Energy Technology Data Exchange (ETDEWEB)

    Tam, P.S.W.

    1986-01-01

    An oxidative-desulfurization (ODS) process was used to remove sulfur from diesel oils. The oxidants used were nitrogen dioxide and nitric acid. The feedstock under investigation was Atmospheric Gas Oil (AGO). Extraction of the oxidized oil with el-butyrolactone was used to remove additional sulfur from the oil. For a given solvent-to-oil (S/O) ratio, the extraction results from oxidized AGO showed higher sulfur removal than from the unoxidized oil. The ODS reactions are chain, free radical, auto-catalytic polymerization reactions similar to those in the sediment formation in fuel oil upon storage. Removal of sulfur by oxidation is from the deposition of co-product (residue) with high sulfur content. Increasing the oxidant concentration leads to increased residue formation, resulting in greater sulfur removal. A mathematical kinetic model is presented to describe the kinetics of sulfur removal in the oxidation of AGO using a CSTR. This model employs lumping of the sulfur compounds in the oil into three groups, according to their retention times in the gas chromatograph. Sulfur and nitrogen compounds usually poison catalysts in hydrocarbon processing. Models were developed to predict the cracking rate and catalyst activity in the cracking of cumene in the presence of organic nitrogen-containing poisons. A new mathematical definition of catalyst activity was used, including the adsorbed poison on active sites. Experimental data were used to fit the derived models, with excellent results. Finally, the use of exponential integral techniques to solve, analytically, the band-aging catalyst deactivation problem in an adiabatic fixed bed reactor is presented.

  3. Modeling the Shock Ignition of a Copper Oxide Aluminum Thermite

    Science.gov (United States)

    Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

    2015-06-01

    An experimental ``striker confinement'' shock compression test was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. The test places a sample of materials such as a thermite mixture of copper oxide and aluminum powders that are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction/diffusion of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces that nominally make copper liquid and aluminum oxide products. We discuss our model of the shock ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model, that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide can predict the events observed at the particle scale in the experiments. Supported by HDTRA1-10-1-0020 (DTRA), N000014-12-1-0555 (ONR).

  4. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M

    2006-11-10

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

  5. Electrothermal model for complete metal-oxide surge arresters

    Energy Technology Data Exchange (ETDEWEB)

    Costa, E. Guedes da; Naidu, S.R. [UFPB, Dept. of Electrical Engineering, Campina Grande, PB (Brazil); Lima, A. Guedes de [CEFET-PB, Dept. of Mechanical Engineering, Joao Pessoa, PB (Brazil)

    2001-01-01

    A computational, electrothermal model for a complete metal-oxide surge arrester based on the implicit form of the finite-differences method is presented. The model is used to calculate the cooling curve after the application of overvoltages and the temperature variations during standard test. The model has been checked against experiments carried out on a test section and a complete surge arrester and the behaviour of a hypothetical surge arrester during standard tests simulated. (Author)

  6. Modeling the viscosity of silicate melts containing manganese oxide

    Directory of Open Access Journals (Sweden)

    Kim Wan-Yi

    2013-01-01

    Full Text Available Our recently developed model for the viscosity of silicate melts is applied to describe and predict the viscosities of oxide melts containing manganese oxide. The model requires three pairs of adjustable parameters that describe the viscosities in three systems: pure MnO, MnO-SiO2 and MnO-Al2O3-SiO2. The viscosity of other ternary and multicomponent silicate melts containing MnO is then predicted by the model without any additional adjustable model parameters. Experimental viscosity data are reviewed for melts formed by MnO with SiO2, Al2O3, CaO, MgO, PbO, Na2O and K2O. The deviation of the available experimental data from the viscosities predicted by the model is shown to be within experimental error limits.

  7. Tribological behavior of hot-pressed boron carbide with oxidation

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The oxidation behavior at 973-1 273 K and the effect of oxidation on the room-temperature tribological properties of hot-pressed boron carbide ceramic were investigated. Oxidized samples were studied by X-ray diffractometer and scanning electron microscopy. It is demonstrated that the oxidation results in the formation of a thin transparent B2O3 film, and the oxide film is severely cracked during cooling due to the thermal expansion mismatch between the oxide film and B4C substrate. B2O3 reacts with moisture in air to form boric acid, which is a kind of solid lubricant. The sliding friction factors of oxidized B4C pair are about 0.05-0.08, compared to 0.25-0.35 of the as-received B4C pair. When the oxidation temperature is up to 1 273 K, severe unstability and increase of friction factor are observed. Visual inspection of the wear track reveals that the lubricant film is broken and some debris particles occur on and around the rubbing surfaces, because the friction interface is rough by the severe etching of grain boundaries.

  8. 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...

  9. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

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

    2005-01-01

    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 m

  10. Animation Model to Conceptualize ATP Generation: A Mitochondrial Oxidative Phosphorylation

    Science.gov (United States)

    Jena, Ananta Kumar

    2015-01-01

    Adenosine triphosphate (ATP) is the molecular unit of intracellular energy and it is the product of oxidative phosphorylation of cellular respiration uses in cellular processes. The study explores the growth of the misconception levels amongst the learners and evaluates the effectiveness of animation model over traditional methods. The data…

  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...

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

    International Nuclear Information System (INIS)

    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)

  13. Mathematical Modeling of Wastewater Oxidation under Microgravity Conditions

    Directory of Open Access Journals (Sweden)

    Boyun Guo

    2005-01-01

    Full Text Available 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 theoretically investigate factors affecting the performance of the VRA reactor under microgravity conditions. The efficiency of catalyst oxidation is controlled by catalyst oxidation kinetics and oxygen gas distribution in the reactor. The process involves bubbly flow in porous media with chemical reactions in a microgravity environment, which has not been previously studied. We have developed and used a mathematical model in this study to simulate the organics oxidation process in the VRA reactor. On the basis of theoretical studies with the model, we conclude that 1 the remaining oxygen gas in the VRA reactor should decline exponentially with reactor length; 2 the decline rate is directly proportional to the rate of oxidation per unit area and bubble sphericity and inversely proportional to bubble size, oxygen density and bubble velocity; and 3 gravity affects oxygen utilization through changing several parameters including oxygen bubble size.

  14. A model for the degradation of polyimides due to oxidation

    OpenAIRE

    Karra, Satish; K.R. Rajagopal

    2010-01-01

    Polyimides, due to their superior mechanical behavior at high temperatures, are used in a variety of applications that include aerospace, automobile and electronic packaging industries, as matrices for composites, as adhesives etc. In this paper, we extend our previous model in [S. Karra, K. R. Rajagopal, Modeling the non-linear viscoelastic response of high temperature polyimides, Mechanics of Materials, In press, doi:10.1016/j.mechmat.2010.09.006], to include oxidative degradation of these ...

  15. 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 ...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute.......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...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  16. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  17. Multi-component transparent conducting oxides: progress in materials modelling

    Science.gov (United States)

    Walsh, Aron; Da Silva, Juarez L. F.; Wei, Su-Huai

    2011-08-01

    Transparent conducting oxides (TCOs) play an essential role in modern optoelectronic devices through their combination of electrical conductivity and optical transparency. We review recent progress in our understanding of multi-component TCOs formed from solid solutions of ZnO, In2O3, Ga2O3 and Al2O3, with a particular emphasis on the contributions of materials modelling, primarily based on density functional theory. In particular, we highlight three major results from our work: (i) the fundamental principles governing the crystal structures of multi-component oxide structures including (In2O3)(ZnO)n and (In2O3)m(Ga2O3)l(ZnO)n; (ii) the relationship between elemental composition and optical and electrical behaviour, including valence band alignments; (iii) the high performance of amorphous oxide semiconductors. On the basis of these advances, the challenge of the rational design of novel electroceramic materials is discussed.

  18. Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling

    NARCIS (Netherlands)

    Zhang, X.; Bieberle, A.

    2016-01-01

    This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/b

  19. 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

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

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-08-01

    Full Text Available Global models of atmospheric mercury generally assume that 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 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 of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model

  1. Oxide thinning percolation statistical model for soft breakdown in ultrathin gate oxides

    Science.gov (United States)

    Chen, Ming-Jer; Kang, Ting-Kuo; Liu, Chuan-Hsi; Chang, Yih J.; Fu, Kuan-Yu

    2000-07-01

    An existing cell-based percolation model with parameter correlation can find its potential applications in assessing soft-breakdown (BD) statistics as long as the oxide thinning due to the localized physical damage near the SiO2/Si interface is accounted for. The resulting model is expressed explicitly with the critical trap number per cell nBD and the remaining oxide thickness tox' both as parameters. Reproduction of time-to-bimodal (soft- and hard-) breakdown statistical data from 3.3-nm-thick gate-oxide samples yields nBD of 3 and 4 for soft and hard breakdown, respectively. The extracted tox' of 1.0 nm for soft breakdown, plus the transition layer thickness of 0.5 nm in the model, is fairly comparable with literature values from current-voltage fitting. The dimension and area of the localized physically damaged region or percolation path (cell) are quantified as well. Based on the work, the origins of soft and hard breakdown are clarified in the following: (i) soft breakdown behaves intrinsically as hard breakdown, that is, they share the same defect (neutral trap) generation process and follow Poisson random statistics; (ii) both are independent events corresponding to different tox' requirements; and (iii) hard breakdown takes place in a certain path located differently from that for the first soft breakdown.

  2. Controllably Inducing and Modeling Optical Response from Graphene Oxide

    Science.gov (United States)

    Lombardo, Nicholas; Naumov, Anton

    Graphene, a novel 2-dimensional sp2-hybridized allotrope of Carbon, has unique electrical and mechanical properties. While it is naturally a highly conductive zero band gap semiconductor, graphene does not exhibit optical emission. It has been shown that functionalization with oxygen-containing groups elicits an opening of band gap in graphene. In this work, we aim to induce an optical response in graphene via controlled oxidation, and then explore potential origins of its photoluminescence through mathematical modeling. We employ timed ozone treatment of initially non-fluorescent reduced graphene oxide (RGO) to produce graphene oxide (GO) with specific optical properties. Oxidized material exhibits substantial changes in the absorption spectra and a broad photoluminescence feature, centered at 532 nm, which suggests the appearance of a band gap. We then explore a number of possible mechanisms for the origin of GO photoluminescence via PM3 and ab initio calculations on a functionalized single sheet of graphene. By adjusting modeling parameters to fit experimentally obtained optical transition energies we estimate the size of the sp2 graphitic regions in GO and the arrangement of functional groups that could be responsible for the observed emission.

  3. Growth Model for Pulsed-Laser Deposited Perovskite Oxide Films

    Institute of Scientific and Technical Information of China (English)

    WANG Xu; FEI Yi-Yan; ZHU Xiang-Dong; Lu Hui-Bin; YANG Guo-Zhen

    2008-01-01

    We present a multi-level growth model that yields some of the key features of perovskite oxide film growth as observed in the reflection high energy electron diffraction(RHEED)and ellipsometry studies.The model describes the effect of deposition,temperature,intra-layer transport,interlayer transport and Ostwald ripening on the morphology of a growth surface in terms of the distribution of terraces and step edges during and after deposition.The numerical results of the model coincide well with the experimental observation.

  4. 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...... physically realistic parameters. Unfortunately the rate expression based on this microkinetic model is complex and impractical to apply for reactor engineering purposes. In this paper the rate expression is simplified by a number of approximations to make it suitable for practical applications without...

  5. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten;

    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...... physically realistic parameters. Unfortunately the rate expression based on this microkinetic model is complex and impractical to apply for reactor engineering purposes. In this paper the rate expression is simplified by a number of approximations to make it suitable for practical applications without...

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

    OpenAIRE

    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 between the properties of the terminal V==O bond and the butane oxidation turnover frequency (TOF) during in situ Raman spectroscopy study. Furthermore, neither the n-butane oxidation TOF nor maleic anhy...

  7. A Cellular Model for Screening Neuronal Nitric Oxide Synthase Inhibitors

    OpenAIRE

    Fang, Jianguo; Silverman, Richard B.

    2009-01-01

    Nitric oxide synthase (NOS) inhibitors are potential drug candidates because it has been well demonstrated that excessive production of NO critically contributes to a range of diseases. Most inhibitors have been screened in vitro using recombinant enzymes, leading to the discovery of a variety of potent compounds. To make inhibition studies more physiologically relevant and bridge the gap between the in vitro assay and in vivo studies, we report here a cellular model for screening NOS inhibit...

  8. Modeling of nitric oxide emissions from temperate agricultural ecosystems.

    OpenAIRE

    Rolland, Marie-Noëlle; Gabrielle, Benoît; Laville, Patricia; Serça, Dominique; Cortinovis, Jérôme; Larmanou, Eric; Lehuger, Simon; Cellier, Pierre

    2006-01-01

    48 p. Arable soils are a significant source of nitric oxide (NO), most of which is derived from nitrogen fertilizers. Precise estimates of NO emissions from these soils are thus essential to devise strategies to mitigate the impact of agriculture on tropospheric ozone regulation. This paper presents the implementation of a soil NO emissions submodel within the environmentally-orientated soil crop model, CERES-EGC. The submodel simulates the NO production via nitrification pathway, as modul...

  9. Assessment of the basis for modeling releases from plutonium oxidation

    International Nuclear Information System (INIS)

    Ideally, a model of the release of plutonium aerosols from plutonium during oxidation or combustion should begin from a description of the plutonium material and its surroundings and proceed unequivocally to a situation-dependent estimate of the amount of oxide released and its size distribution. Such a model would need to provide a description of the heat- and mass-transfer processes involved and link them directly to the rate of aerosol production. The first step, the description of heat and mass transfer, is more easily achieved from current information than the second, the aerosol release. The sections of this report titled ''Physical Fundamentals'' and ''Available Theoretical Information'' describe the approach that would be required for theoretical modeling. The ''Experimental Results'' section describes the information on aerosol releases, size distributions, peak temperatures, oxidation rates, and experimental conditions that we have gleaned from the existing experimental literature. The data is summarized and the bibliography lists the relevant literature that has and has not been reviewed. 42 refs., 10 figs., 6 tabs

  10. Growth model of lantern-like amorphous silicon oxide nanowires

    Science.gov (United States)

    Wu, Ping; Zou, Xingquan; Chi, Lingfei; Li, Qiang; Xiao, Tan

    2007-03-01

    Silicon oxide nanowire assemblies with lantern-like morphology were synthesized by thermal evaporation of the mixed powder of SnO2 and active carbon at 1000 °C and using the silicon wafer as substrate and source. The nano-lanterns were characterized by a scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), energy-dispersive spectroscope (EDS) and selective area electron diffraction (SAED). The results show that the nano-lantern has symmetrical morphology, with one end connecting with the silicon wafer and the other end being the tin ball. The diameter of the nano-lantern is about 1.5-3.0 µm. Arc silicon oxide nanowire assemblies between the two ends have diameters ranging from 70 to 150 nm. One single catalyst tin ball catalyzes more than one amorphous nanowires' growth. In addition, the growth mechanism of the nano-lantern is discussed and a growth model is proposed. The multi-nucleation sites round the Sn droplet's perimeter are responsible for the formation of many SiOx nanowires. The growing direction of the nanowires is not in the same direction of the movement of the catalyst tin ball, resulting in the bending of the nanowires and forming the lantern-like silicon oxide morphology. The controllable synthesis of the lantern-like silicon oxide nanostructure may have potential applications in the photoelectronic devices field.

  11. Growth model of lantern-like amorphous silicon oxide nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Wu Ping; Zou Xingquan; Chi Lingfei; Li Qiang; Xiao Tan [Department of Physics, Shantou University, Shantou 515063 (China)

    2007-03-28

    Silicon oxide nanowire assemblies with lantern-like morphology were synthesized by thermal evaporation of the mixed powder of SnO{sub 2} and active carbon at 1000 deg. C and using the silicon wafer as substrate and source. The nano-lanterns were characterized by a scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), energy-dispersive spectroscope (EDS) and selective area electron diffraction (SAED). The results show that the nano-lantern has symmetrical morphology, with one end connecting with the silicon wafer and the other end being the tin ball. The diameter of the nano-lantern is about 1.5-3.0 {mu}m. Arc silicon oxide nanowire assemblies between the two ends have diameters ranging from 70 to 150 nm. One single catalyst tin ball catalyzes more than one amorphous nanowires' growth. In addition, the growth mechanism of the nano-lantern is discussed and a growth model is proposed. The multi-nucleation sites round the Sn droplet's perimeter are responsible for the formation of many SiO{sub x} nanowires. The growing direction of the nanowires is not in the same direction of the movement of the catalyst tin ball, resulting in the bending of the nanowires and forming the lantern-like silicon oxide morphology. The controllable synthesis of the lantern-like silicon oxide nanostructure may have potential applications in the photoelectronic devices field.

  12. 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...

  13. A model for the thermo-oxidative degradation of polyimides

    Science.gov (United States)

    Karra, Satish; Rajagopal, K. R.

    2012-08-01

    Polyimides, due to their superior mechanical behavior at high temperatures, are used in a variety of applications that include aerospace, automobile and electronic packaging industries, as matrices for composites, as adhesives etc. In this paper, we extend our previous model in S. Karra and K. Rajagopal (Mech. Mater. 43(1):54-61, 2011), to include thermo-oxidative degradation of these high temperature polyimides. Appropriate forms for the Helmholtz potential and the rate of dissipation are chosen to describe the degradation. The results for a specific boundary value problem, using our model, compares well with the experimental creep data for PMR-15 resin that is aged in air.

  14. 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 betwee

  15. 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 of...... modeling parameters are fit to the many processes which often overlap in the same frequency ranges. Also, commonly used equivalent circuit (EC) models only provide zero-dimensional (0-D) approximations of the processes of the two electrodes, electrolyte and gas transport. Employing improved analytical...... 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...

  16. 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.

  17. Density functional theory modeling of multilayer "epitaxial" graphene oxide.

    Science.gov (United States)

    Zhou, Si; Bongiorno, Angelo

    2014-11-18

    CONSPECTUS: Graphene oxide (GO) is a complex material of both fundamental and applied interest. Elucidating the structure of GO is crucial to achieve control over its properties and technological applications. GO is a nonstoichiometric and hygroscopic material with a lamellar structure, and its physical chemical properties depend critically on synthesis procedures and postsynthesis treatments. Numerous efforts are in place to both understand and exploit this versatile layered carbon material. This Account reports on recent density functional theory (DFT) studies of "epitaxial" graphene oxide (hereafter EGO), a type of GO obtained by oxidation of graphene films grown epitaxially on silicon carbide. Here, we rely on selected X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), and X-ray diffraction (XRD) measurements of EGO, and we discuss in great detail how we utilized DFT-based techniques to project out from the experimental data basic atomistic information about the chemistry and structure of these films. This Account provides an example as to how DFT modeling can be used to elucidate complex materials such as GO from a limited set of experimental information. EGO exhibits a uniform layered structure, consisting of a stack of graphene planes hosting predominantly epoxide and hydroxyl groups, and water molecules intercalated between the oxidized carbon layers. Here, we first focus on XPS measurements of EGO, and we use DFT to generate realistic model structures, calculate core-level chemical shifts, and through the comparison with experiment, gain insight on the chemical composition and metastability characteristics of EGO. DFT calculations are then used to devise a simplistic but accurate simulation scheme to study thermodynamic and kinetic stability and to predict the intralayer structure of EGO films aged at room temperature. Our simulations show that aged EGO encompasses layers with nanosized oxidized domains presenting a high concentration of

  18. Oxidative airway inflammation leads to systemic and vascular oxidative stress in a murine model of allergic asthma.

    Science.gov (United States)

    Al-Harbi, Naif O; Nadeem, A; Al-Harbi, Mohamed M; Imam, F; Al-Shabanah, Othman A; Ahmad, Sheikh F; Sayed-Ahmed, Mohamed M; Bahashwan, Saleh A

    2015-05-01

    Oxidant-antioxidant imbalance plays an important role in repeated cycles of airway inflammation observed in asthma. It is when reactive oxygen species (ROS) overwhelm antioxidant defenses that a severe inflammatory state becomes apparent and may impact vasculature. Several studies have shown an association between airway inflammation and cardiovascular complications; however so far none has investigated the link between airway oxidative stress and systemic/vascular oxidative stress in a murine model of asthma. Therefore, this study investigated the contribution of oxidative stress encountered in asthmatic airways in modulation of vascular/systemic oxidant-antioxidant balance. Rats were sensitized intraperitoneally with ovalbumin (OVA) in the presence of aluminum hydroxide followed by several intranasal (i.n.) challenges with OVA. Rats were then assessed for airway and vascular inflammation, oxidative stress (ROS, lipid peroxides) and antioxidants measured as total antioxidant capacity (TAC) and thiol content. Challenge with OVA led to increased airway inflammation and oxidative stress with a concomitant increase in vascular inflammation and oxidative stress. Oxidative stress in the vasculature was significantly inhibited by antioxidant treatment, N-acetyl cysteine; whereas hydrogen peroxide (H2O2) inhalation worsened it. Therefore, our study shows that oxidative airway inflammation is associated with vascular/systemic oxidative stress which might predispose these patients to increased cardiovascular risk.

  19. Evidence of Oxidative Stress in Autism Derived from Animal Models

    Directory of Open Access Journals (Sweden)

    Xue Ming

    2008-01-01

    Full Text Available Autism is a pervasive neurodevelopmental disorder that leads to deficits in social interaction, communication and restricted, repetitive motor movements. Autism is a highly heritable disorder, however, there is mounting evidence to suggest that toxicant-induced oxidative stress may play a role. The focus of this article will be to review our animal model of autism and discuss our evidence that oxidative stress may be a common underlying mechanism of neurodevelopmental damage. We have shown that mice exposed to either methylmercury (MeHg or valproic acid (VPA in early postnatal life display aberrant social, cognitive and motor behavior. Interestingly, early exposure to both compounds has been clinically implicated in the development of autism. We recently found that Trolox, a water-soluble vitamin E derivative, is capable of attenuating a number of neurobehavioral alterations observed in mice postnatally exposed to MeHg. In addition, a number of other investigators have shown that oxidative stress plays a role in neural injury following MeHg exposure both in vitro and in vivo. New data presented here will show that VPA-induced neurobehavioral deficits are attenuated by vitamin E as well and that the level of glial fibrillary acidic protein (GFAP, a marker of astrocytic neural injury, is altered following VPA exposure. Collectively, these data indicate that vitamin E and its derivative are capable of protecting against neurobehavioral deficits induced by both MeHg and VPA. This antioxidant protection suggests that oxidative stress may be a common mechanism of injury leading to aberrant behavior in both our animal model as well as in the human disease state.

  20. 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.

  1. Modeling toxic compounds from nitric oxide emission measurements

    Science.gov (United States)

    Vallero, Daniel A.; Peirce, Jeffrey; Cho, Ki Don

    Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.

  2. Macro Level Modeling of a Tubular Solid Oxide Fuel Cell

    Directory of Open Access Journals (Sweden)

    Farshid Zabihian

    2010-11-01

    Full Text Available This paper presents a macro-level model of a solid oxide fuel cell (SOFC stack implemented in Aspen Plus® for the simulation of SOFC system. The model is 0-dimensional and accepts hydrocarbon fuels such as reformed natural gas, with user inputs of current density, fuel and air composition, flow rates, temperature, pressure, and fuel utilization factor. The model outputs the composition of the exhaust, work produced, heat available for the fuel reformer, and electrochemical properties of SOFC for model validation. It was developed considering the activation, concentration, and ohmic losses to be the main over-potentials within the SOFC, and mathematical expressions for these were chosen based on available studies in the literature. The model also considered the water shift reaction of CO and the methane reforming reaction. The model results were validated using experimental data from Siemens Westinghouse. The results showed that the model could capture the operating pressure and temperature dependency of the SOFC performance successfully in an operating range of 1–15 atm for pressure and 900 °C–1,000 °C for temperature. Furthermore, a sensitivity analysis was performed to identify the model constants and input parameters that impacted the over-potentials.

  3. Modeling the oxidation of phenolic compounds by hydrogen peroxide photolysis.

    Science.gov (United States)

    Zhang, Tianqi; Cheng, Long; Ma, Lin; Meng, Fanchao; Arnold, Robert G; Sáez, A Eduardo

    2016-10-01

    Hydrogen peroxide UV photolysis is among the most widely used advanced oxidation processes (AOPs) for the destruction of trace organics in waters destined for reuse. Previous kinetic models of hydrogen peroxide photolysis focus on the dynamics of hydroxyl radical production and consumption, as well as the reaction of the target organic with hydroxyl radicals. However, the rate of target destruction may also be affected by radical scavenging by reaction products. In this work, we build a predictive kinetic model for the destruction of p-cresol by hydrogen peroxide photolysis based on a complete reaction mechanism that includes reactions of intermediates with hydroxyl radicals. The results show that development of a predictive kinetic model to evaluate process performance requires consideration of the complete reaction mechanism, including reactions of intermediates with hydroxyl radicals. PMID:27448315

  4. 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...... physical parameters such as the cathode thickness. ©2010 COPYRIGHT ECS - The Electrochemical Society...

  5. Mechanical modeling of porous oxide fuel pellet A Test Problem

    Energy Technology Data Exchange (ETDEWEB)

    Nukala, Phani K [ORNL; Barai, Pallab [ORNL; Simunovic, Srdjan [ORNL; Ott, Larry J [ORNL

    2009-10-01

    A poro-elasto-plastic material model has been developed to capture the response of oxide fuels inside the nuclear reactors under operating conditions. Behavior of the oxide fuel and variation in void volume fraction under mechanical loading as predicted by the developed model has been reported in this article. The significant effect of void volume fraction on the overall stress distribution of the fuel pellet has also been described. An important oxide fuel issue that can have significant impact on the fuel performance is the mechanical response of oxide fuel pellet and clad system. Specifically, modeling the thermo-mechanical response of the fuel pellet in terms of its thermal expansion, mechanical deformation, swelling due to void formation and evolution, and the eventual contact of the fuel with the clad is of significant interest in understanding the fuel-clad mechanical interaction (FCMI). These phenomena are nonlinear and coupled since reduction in the fuel-clad gap affects thermal conductivity of the gap, which in turn affects temperature distribution within the fuel and the material properties of the fuel. Consequently, in order to accurately capture fuel-clad gap closure, we need to account for fuel swelling due to generation, retention, and evolution of fission gas in addition to the usual thermal expansion and mechanical deformation. Both fuel chemistry and microstructure also have a significant effect on the nucleation and growth of fission gas bubbles. Fuel-clad gap closure leading to eventual contact of the fuel with the clad introduces significant stresses in the clad, which makes thermo-mechanical response of the clad even more relevant. The overall aim of this test problem is to incorporate the above features in order to accurately capture fuel-clad mechanical interaction. Because of the complex nature of the problem, a series of test problems with increasing multi-physics coupling features, modeling accuracy, and complexity are defined with the

  6. 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.)

  7. MODEL-BASED STUDY OF OXIDATION PROCESSES IN A JET ENGINE FUEL LIQUID PHASE

    OpenAIRE

    Orlovskaya, N.; Shupranov, D.; Bezborodov, Yu; Nadeykin, I.

    2009-01-01

    The process of oxidation in hexadecane liquid phase as a conventional model of oil hydrocarbons is investigated. The oxidation product structure is defined by means of Chromatography/Mass Spectrometry.

  8. A Simple Hydraulic Analog Model of Oxidative Phosphorylation.

    Science.gov (United States)

    Willis, Wayne T; Jackman, Matthew R; Messer, Jeffrey I; Kuzmiak-Glancy, Sarah; Glancy, Brian

    2016-06-01

    Mitochondrial oxidative phosphorylation is the primary source of cellular energy transduction in mammals. This energy conversion involves dozens of enzymatic reactions, energetic intermediates, and the dynamic interactions among them. With the goal of providing greater insight into the complex thermodynamics and kinetics ("thermokinetics") of mitochondrial energy transduction, a simple hydraulic analog model of oxidative phosphorylation is presented. In the hydraulic model, water tanks represent the forward and back "pressures" exerted by thermodynamic driving forces: the matrix redox potential (ΔGredox), the electrochemical potential for protons across the mitochondrial inner membrane (ΔGH), and the free energy of adenosine 5'-triphosphate (ATP) (ΔGATP). Net water flow proceeds from tanks with higher water pressure to tanks with lower pressure through "enzyme pipes" whose diameters represent the conductances (effective activities) of the proteins that catalyze the energy transfer. These enzyme pipes include the reactions of dehydrogenase enzymes, the electron transport chain (ETC), and the combined action of ATP synthase plus the ATP-adenosine 5'-diphosphate exchanger that spans the inner membrane. In addition, reactive oxygen species production is included in the model as a leak that is driven out of the ETC pipe by high pressure (high ΔGredox) and a proton leak dependent on the ΔGH for both its driving force and the conductance of the leak pathway. Model water pressures and flows are shown to simulate thermodynamic forces and metabolic fluxes that have been experimentally observed in mammalian skeletal muscle in response to acute exercise, chronic endurance training, and reduced substrate availability, as well as account for the thermokinetic behavior of mitochondria from fast- and slow-twitch skeletal muscle and the metabolic capacitance of the creatine kinase reaction.

  9. A Simple Hydraulic Analog Model of Oxidative Phosphorylation.

    Science.gov (United States)

    Willis, Wayne T; Jackman, Matthew R; Messer, Jeffrey I; Kuzmiak-Glancy, Sarah; Glancy, Brian

    2016-06-01

    Mitochondrial oxidative phosphorylation is the primary source of cellular energy transduction in mammals. This energy conversion involves dozens of enzymatic reactions, energetic intermediates, and the dynamic interactions among them. With the goal of providing greater insight into the complex thermodynamics and kinetics ("thermokinetics") of mitochondrial energy transduction, a simple hydraulic analog model of oxidative phosphorylation is presented. In the hydraulic model, water tanks represent the forward and back "pressures" exerted by thermodynamic driving forces: the matrix redox potential (ΔGredox), the electrochemical potential for protons across the mitochondrial inner membrane (ΔGH), and the free energy of adenosine 5'-triphosphate (ATP) (ΔGATP). Net water flow proceeds from tanks with higher water pressure to tanks with lower pressure through "enzyme pipes" whose diameters represent the conductances (effective activities) of the proteins that catalyze the energy transfer. These enzyme pipes include the reactions of dehydrogenase enzymes, the electron transport chain (ETC), and the combined action of ATP synthase plus the ATP-adenosine 5'-diphosphate exchanger that spans the inner membrane. In addition, reactive oxygen species production is included in the model as a leak that is driven out of the ETC pipe by high pressure (high ΔGredox) and a proton leak dependent on the ΔGH for both its driving force and the conductance of the leak pathway. Model water pressures and flows are shown to simulate thermodynamic forces and metabolic fluxes that have been experimentally observed in mammalian skeletal muscle in response to acute exercise, chronic endurance training, and reduced substrate availability, as well as account for the thermokinetic behavior of mitochondria from fast- and slow-twitch skeletal muscle and the metabolic capacitance of the creatine kinase reaction. PMID:26807634

  10. 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.

  11. 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

  12. Photosynthetic water oxidation: insights from manganese model chemistry.

    Science.gov (United States)

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond

  13. Photosynthetic water oxidation: insights from manganese model chemistry.

    Science.gov (United States)

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond

  14. Methane oxidation and methanotrophs: resistance and resilience against model perturbations

    Science.gov (United States)

    Ho, A.; Frenzel, P.

    2009-04-01

    Biodiversity is claimed to be essential for ecosystem functioning. However, most experiments on biodiversity and ecosystem functioning (BEF) have been made on higher plants, while only few studies have dealt with microbial communities. Overall microbial diversity may be very high, and general functions like aerobic carbon mineralization are assumed to be supported by highly redundant communities. Therefore, we focused on methane oxidation, a microbial process of global importance mitigating methane emissions from wetland, rice fields, and landfills. We used a rice paddy as our model system, where >90% of potentially emitted methane may be oxidized in the oxic surface layer. This community is presumed to consist of 10-20 taxa more or less equivalent to species. We focused on the ability of methanotrophs to recover from a disturbance causing a significant die-off of all microbial populations. This was simulated by mixing native with sterile soil in two ratios (1:4 and 1:40). Microcosms were incubated and the temporal shift of the methanotrophic communities was followed by pmoA-based Terminal Restriction Length Polymorphism (T-RFLP), qPCR, and a pmoA-based diagnostic microarray. We consistently observed distinctive temporal shifts between Methylocystaceaea and Methylococcacea, a rapid population growth leading to the same or even higher cell numbers as in microcosms made from native soil alone, but no effect on the amount of methane oxidized. The ratio of different methanotrophs changed with treatment, while the number of taxa stayed nearly the same. Overall, methanotrophs showed a remarkable resilience compensating for die-offs. It has to be noted, however, that our experiment focused on methanotrophs adapted to and living at high methane fluxes. Quite different, methanotrophs living in upland soils do not mitigate methane emissions, but are the only biological sink to atmospheric methane. These microbes are severely substrate limited, and will be much more

  15. 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.

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

    DEFF Research Database (Denmark)

    Berner, Torben Sune; Arneborg, Nils

    2012-01-01

    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...... 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...... 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...

  17. Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling.

    Science.gov (United States)

    Zhang, Xueqing; Bieberle-Hütter, Anja

    2016-06-01

    This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/band edge, charge transport, and electrochemical reactions at the electrode-electrolyte interface. In particular, we review the mechanisms of the oxygen evolution reaction, strategies to lower overpotential, and computational methods applied to PEC systems with particular focus on multiscale modeling. The current challenges in modeling PEC interfaces and their processes are summarized. At the end, we propose a new multiscale modeling approach to simulate the PEC interface under conditions most similar to those of experiments. This approach will contribute to identifying the limitations at PEC interfaces. Its generic nature allows its application to a number of electrochemical systems.

  18. Systemic Oxidative Stress markers in animal model for Depression

    DEFF Research Database (Denmark)

    Bouzinova, Elena

    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...

  19. Experimental and modeling study of the oxidation of xylenes

    CERN Document Server

    Battin-Leclerc, F; Glaude, P A; Belmekki, N; Battin-Leclerc, Fr\\'{e}d\\'{e}rique; Bounaceur, Roda; Glaude, Pierre-Alexandre; Belmekki, Najib

    2006-01-01

    This paper describes an experimental and modeling study of the oxidation of the three isomers of xylene (ortho-, meta- and para-xylenes). For each compound, ignition delay times of hydrocarbon-oxygen-argon mixtures with fuel equivalence ratios from 0.5 to 2 were measured behind reflected shock waves for temperatures from 1330 to 1800 K and pressures from 6.7 to 9 bar. The results show a similar reactivity for the three isomers. A detailed kinetic mechanism has been proposed, which reproduces our experimental results, as well as some literature data obtained in a plug flow reactor at 1155 K showing a clear difference of reactivity between the three isomers of xylene. The main reaction paths have been determined by sensitivity and flux analyses and have allowed the differences of reactivity to be explained.

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

    NARCIS (Netherlands)

    Albrecht, Bogdan Alexandru

    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

  1. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.; Graaff, M. de; Bosch, P.L. van den; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.W.M.

    2013-01-01

    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 concl

  2. An approach to modeling of silicon oxidation in a wet ultra-diluted ambient

    NARCIS (Netherlands)

    Kovalgin, A.Y.; Hof, A.J.; Schmitz, J.

    2005-01-01

    In this work, we make steps towards developing a new wet-oxidation model of silicon based on electron-stimulated dissociation of H2O molecules. The need for a new model arises from the fact that existing physical models are inadequate to describe the thin-oxide regime. Two regimes of silicon oxidati

  3. 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.

  4. 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

  5. Protective Effect of Arginine on Oxidative Stress in Transgenic Sickle Mouse Models

    OpenAIRE

    Dasgupta, Trisha; Hebbel, Robert P.; Kaul, Dhananjay K.

    2006-01-01

    Sickle cell disease (SCD) is characterized by reperfusion injury and chronic oxidative stress. Oxidative stress and hemolysis in SCD result in inactivation of nitric oxide (NO) and depleted arginine levels. We hypothesized that augmenting NO production by arginine supplementation will reduce oxidative stress in SCD. To this end, we measured the effect of arginine (5% in mouse chow) on NO metabolites (NOx), lipid peroxidation (LPO) and selected antioxidants in transgenic sickle mouse models. U...

  6. Modeling the chemical evolution of nitrogen oxides near roadways

    Science.gov (United States)

    Wang, Yan Jason; DenBleyker, Allison; McDonald-Buller, Elena; Allen, David; Zhang, K. Max

    2011-01-01

    The chemical evolution of nitrogen dioxide (NO 2) and nitrogen monoxide (NO) in the vicinity of roadways is numerically investigated using a computational fluid dynamics model, CFD-VIT-RIT and a Gaussian-based model, CALINE4. CFD-VIT-RIT couples a standard k- ɛ turbulence model for turbulent mixing and the Finite-Rate model for chemical reactions. CALINE4 employs a discrete parcel method, assuming that chemical reactions are independent of the dilution process. The modeling results are compared to the field measurement data collected near two roadways in Austin, Texas, State Highway 71 (SH-71) and Farm to Market Road 973 (FM-973), under parallel and perpendicular wind conditions during the summer of 2007. In addition to ozone (O 3), other oxidants and reactive species including hydroperoxyl radical (HO 2), organic peroxyl radical (RO 2), formaldehyde (HCHO) and acetaldehyde (CH 3CHO) are considered in the transformation from NO to NO 2. CFD-VIT-RIT is shown to be capable of predicting both NO x and NO 2 profiles downwind. CALINE4 is able to capture the NO x profiles, but underpredicts NO 2 concentrations under high wind velocity. Our study suggests that the initial NO 2/NO x ratios have to be carefully selected based on traffic conditions in order to assess NO 2 concentrations near roadways. The commonly assumed NO 2/NO x ratio by volume of 5% may not be suitable for most roadways, especially those with a high fraction of heavy-duty truck traffic. In addition, high O 3 concentrations and high traffic volumes would lead to the peak NO 2 concentration occurring near roadways with elevated concentrations persistent over a long distance downwind.

  7. Modeling of structural effects in biomedical elements after titanium oxidation in fluidized bed

    Directory of Open Access Journals (Sweden)

    Mendzik K.

    2010-06-01

    Full Text Available Oxidation is one of the most employed methods to improve titanium and its alloys properties especially due to medical application. This process like most of the thermochemical treatment processes substantially influences on the characteristic of surface layers and the same on its mechanical and useful properties. Oxide coatings produced during titanium oxidation were examined due to their composition identification. Titanium was oxidized in fluidized bed in temperature range between 500÷700°C. Microstructures of titanium with a visible oxide coating on its surface after thermochemical treatment and changes of grain size in core of titanium samples are described. Moreover Xray phase analysis of obtained oxides coatings was made as well as microhardness measurements of titanium surface layers after oxidation process. Finally, the surfaces of titanium after oxidation in fluidized bed were measured by Auger electron spectroscopy. All research results are used to built numerical model of oxidation process in fluidized. Titanium oxidation process in fluidized bed is very complicated, because changes of parameters are non linear characteristics. This fact and lack of mathematical algorithms describing this process makes modeling properties of titanium elements by traditional numerical methods difficult or even impossible. In this case it is possible to try using artificial neural network. Using neural networks for modeling oxidizing in fluidized bed is caused by several nets' features: non linear character, ability to generalize the results of calculations for data out of training set, no need for mathematical algorithms describing influence changes input parameters on modeling materials properties.

  8. 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

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

    International Nuclear Information System (INIS)

    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)O2 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 CeO2 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 Cr2O3 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)

  10. Electro oxidation of Malachite Green and Modeling Using ANN

    OpenAIRE

    Antony Soloman, P.; Ahmed Basha, C.; Velan, M.; Balasubramanian, N.

    2010-01-01

    This study involves the electro-oxidation of malachite green, a triphenyl methane dye, extensively used in industries and aquaculture, and later banned in most developed countries because of its potential carcinogenicity, mutagenicity and teratogenicity in mammals. The study is conducted in a batch electro-chemical reactor using the catalytic anode (made of noble oxide coated, RuOx-TiOx, titanium expanded mesh) that mediates the oxidation of organic species by the formation of higher oxida...

  11. Stoichiometric modeling of oxidation of reduced inorganic sulfur compounds (Riscs) in Acidithiobacillus thiooxidans.

    Science.gov (United States)

    Bobadilla Fazzini, Roberto A; Cortés, Maria Paz; Padilla, Leandro; Maturana, Daniel; Budinich, Marko; Maass, Alejandro; Parada, Pilar

    2013-08-01

    The prokaryotic oxidation of reduced inorganic sulfur compounds (RISCs) is a topic of utmost importance from a biogeochemical and industrial perspective. Despite sulfur oxidizing bacterial activity is largely known, no quantitative approaches to biological RISCs oxidation have been made, gathering all the complex abiotic and enzymatic stoichiometry involved. Even though in the case of neutrophilic bacteria such as Paracoccus and Beggiatoa species the RISCs oxidation systems are well described, there is a lack of knowledge for acidophilic microorganisms. Here, we present the first experimentally validated stoichiometric model able to assess RISCs oxidation quantitatively in Acidithiobacillus thiooxidans (strain DSM 17318), the archetype of the sulfur oxidizing acidophilic chemolithoautotrophs. This model was built based on literature and genomic analysis, considering a widespread mix of formerly proposed RISCs oxidation models combined and evaluated experimentally. Thiosulfate partial oxidation by the Sox system (SoxABXYZ) was placed as central step of sulfur oxidation model, along with abiotic reactions. This model was coupled with a detailed stoichiometry of biomass production, providing accurate bacterial growth predictions. In silico deletion/inactivation highlights the role of sulfur dioxygenase as the main catalyzer and a moderate function of tetrathionate hydrolase in elemental sulfur catabolism, demonstrating that this model constitutes an advanced instrument for the optimization of At. thiooxidans biomass production with potential use in biohydrometallurgical and environmental applications.

  12. The oxidative response in the chronic constriction injury model of neuropathic pain.

    NARCIS (Netherlands)

    Tan, E.C.T.H.; Bahrami, S.; Kozlov, A.V.; Kurvers, H.A.J.M.; Laak, H.J. ter; Nohl, H.; Redl, H.; Goris, R.J.A.

    2009-01-01

    BACKGROUND: In the chronic constriction injury model of rat neuropathic pain, oxidative stress as well as antioxidants superoxide dismutase and reduced glutathione (GSH) are important determinants of neuropathological and behavioral consequences. Studies of the chronic constriction injury model obse

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

    Science.gov (United States)

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-01

    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. PMID:27214003

  14. 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.

  15. Copper Oxide Nanoparticles for Advanced Refrigerant Thermophysical Properties: Mathematical Modeling

    Directory of Open Access Journals (Sweden)

    S. A. Fadhilah

    2014-01-01

    Full Text Available In modern days, refrigeration systems are important for industrial and domestic applications. The systems consume more electricity as compared to other appliances. The refrigeration systems have been investigated thoroughly in many ways to reduce the energy consumption. Hence, nanorefrigerant which is one kind of nanofluids has been introduced as a superior properties refrigerant that increased the heat transfer rate in the refrigeration system. Many types of materials could be used as the nanoparticles to be suspended into the conventional refrigerants. In this study, the effect of the suspended copper oxide (CuO nanoparticles into the 1,1,1,2-tetrafluoroethane, R-134a is investigated by using mathematical modeling. The investigation includes the thermal conductivity, dynamic viscosity, and heat transfer rate of the nanorefrigerant in a tube of evaporator. The results show enhanced thermophysical properties of nanorefrigerant compared to the conventional refrigerant. These advanced thermophysical properties increased the heat transfer rate in the tube. The nanorefrigerant could be a potential working fluid to be used in the refrigeration system to increase the heat transfer characteristics and save the energy usage.

  16. Energy dependent model of a metal oxide surge arrester. Sanka aengata hiraiki no energy izon model

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, S.; Kan, M.; Masuzawa, K. (Toshiba Corp., Tokyo (Japan))

    1994-03-20

    This paper reports on modeling a zinc-oxide lightning arrester. The paper indicates that it is difficult to model the zinc-oxide elements by using non-linear resistance and inductance only, based on results of measuring hysteresis curves of restriction voltage on dual peak discharge of the elements. The paper then proposes a model (of numerical expression) that incorporates a concept that the restriction voltage decreases in response to energy absorbed by the elements from the discharge current. The paper explains a method for deciding on constants contained in the proposed expression, and a method to calculate the restriction voltage according to the proposed expression by using TACS of the program EMTP for circuit analysis. Further, it is indicated that the measured values of the restriction voltage on the dual-peak discharge current agree well with the calculated values from the proposed expression. A comparison was made on effects of this model and the conventional non-linear resistance model on the results of analyzing lightning surge responses in a 500-kV model system. 6 refs., 14 figs., 1 tab.

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

    International Nuclear Information System (INIS)

    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

  18. Observations and Model Analysis of Enhanced Oxidized Mercury in the Free Troposphere during NOMADSS

    Science.gov (United States)

    Gratz, L.; Shah, V.; Ambrose, J. L., II; Jaffe, D. A.; Jaegle, L.; Selin, N. E.; Song, S.; Festa, J.; Stutz, J.

    2014-12-01

    Mercury (Hg) is a hazardous neurotoxic pollutant with complex atmospheric speciation and chemistry. It exists in the atmosphere primarily as gaseous elemental Hg (GEM), with a lifetime on the order of months, while oxidized Hg is more water soluble and deposits readily. Thus, Hg is considered both a local and a global pollutant. There are significant limitations in our understanding of global Hg cycling, including the sources and chemical mechanisms producing enhanced oxidized Hg in the free troposphere. Ground-based and airborne studies have associated free tropospheric oxidized Hg with GEM oxidation and atmospheric subsidence. Chemical transport models suggest that free tropospheric GEM oxidation is largely attributable to bromine (Br) atoms. During the 2013 Nitrogen Oxidants Mercury and Aerosol Distributions Sources and Sinks (NOMADSS) campaign, we sought to quantify the distribution and chemical transformation of Hg species in the free troposphere over the southeastern US. Enhanced oxidized Hg over North Texas was associated with long-range transport and subsidence from the sub-tropical Pacific free troposphere, where GEOS-Chem predicts air enriched in oxidized Hg. Bromine oxide (BrO) concentrations were also elevated over North Texas, perhaps supporting halogen oxidation as a source of free tropospheric oxidized Hg. Over the Atlantic Ocean, oxidized Hg up to 680 pg m-3 was associated with GEM oxidation and subsidence within the Atlantic high pressure system. The standard GEOS-Chem model underestimates free tropospheric oxidized Hg in these locations by a factor of three to ten, possibly due to underestimation of Br concentrations and/or uncertainty in the Hg+Br rate constant. We investigate GEOS-Chem's improved ability to reproduce the observed concentrations by tripling free tropospheric Br in the tropics and implementing a faster Hg+Br oxidation mechanism. Results have important implications for our understanding of global-scale atmospheric Hg chemistry and

  19. 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

  20. Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

    Science.gov (United States)

    Jensen, Henriette Stokbro; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2009-04-01

    Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

  1. Inhibition of oxidation in nuclear graphite

    International Nuclear Information System (INIS)

    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 (B4C) indicate that oxidation is dramatically reduced even at prolonged exposures at temperatures up to 900 deg. C. The proposed addition of B4C 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)

  2. Geochemical modelling of arsenic adsorption to oxide surfaces

    OpenAIRE

    Gustafsson, Jon Petter; Bhattacharya, Prosun

    2007-01-01

    In natural environments, arsenic chemistry is dominated by the reactions of its two predominant soluble forms, arsenate and arsenite. To predict the fate of As in the environment, it is necessary to consider processes that act to restrict its mobility. The mobility of As is strongly influenced by adsorption reactions to particle surfaces. Arsenate and arsenite may form surface complexes with a number of different oxides, including Fe-, Al-, Mn- and Ti oxides. The focus of this chapter is on t...

  3. 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. PMID:26426294

  4. Quantitative Mapping of Reversible Mitochondrial Complex I Cysteine Oxidation in a Parkinson Disease Mouse Model*

    OpenAIRE

    Danielson, Steven R.; Held, Jason M.; Oo, May; Riley, Rebeccah; Gibson, Bradford W.; Andersen, Julie K.

    2011-01-01

    Differential cysteine oxidation within mitochondrial Complex I has been quantified in an in vivo oxidative stress model of Parkinson disease. We developed a strategy that incorporates rapid and efficient immunoaffinity purification of Complex I followed by differential alkylation and quantitative detection using sensitive mass spectrometry techniques. This method allowed us to quantify the reversible cysteine oxidation status of 34 distinct cysteine residues out of a total 130 present in muri...

  5. Biogeochemical modelling of anaerobic vs. aerobic methane oxidation in a meromictic crater lake (Lake Pavin, France)

    International Nuclear Information System (INIS)

    Methane is a powerful greenhouse gas and its concentration in the atmosphere has increased over the past decades. Methane produced by methanogenic Archae can be consumed through aerobic and anaerobic oxidation pathways. In anoxic conditions found in freshwater environments such as meromictic lakes, CH4 oxidation pathways involving different terminal electron acceptors such as NO3-, SO42-, and oxides of Fe and Mn are thermodynamically possible. In this study, a reactive transport model was developed to assess the relative significance of the different pathways of CH4 consumption in the water column of Lake Pavin. In most cases, the model reproduced experimental data collected from the field from June 2006 to June 2007. Although the model and the field measurements suggest that anaerobic CH4 oxidation may contribute to CH4 consumption in the water column of Lake Pavin, aerobic oxidation remains the major sink of CH4 in this lake.

  6. Experimental kinetic study and modeling of calcium oxide carbonation

    International Nuclear Information System (INIS)

    Anthropogenic carbon dioxide (CO2) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO2 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 CO2, 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 CO2 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 CO2 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 CaCO3 which causes a change in the porosity

  7. Global modelling of the ClNO2 production impact on tropospheric nitrogen oxides and main oxidants

    Science.gov (United States)

    Cuevas Rodríguez, Carlos Alberto; Brown, Steven S.; Lamarque, Jean-Francoise; Saiz-Lopez, Alfonso; Kinnison, Douglas E.; Lopez-Hilfiker, Felipe; Thornton, Joel A.; Jaegle, Lyatt; Fibiger, Dorothy; McDuffie, Erin E.; Sullivan, Amy P.; Weber, Rodney J.; Dibb, Jack

    2016-04-01

    Heterogeneous uptake of dinitrogen pentoxide, N2O5, to aerosol is one of the most important reactions controlling the global budget of nitrogen oxides, with subsequent impacts on oxidants such as ozone and hydroxyl radical. Most chemistry global models assume that this uptake proceeds through hydrolysis to produce nitric acid, effectively a terminal sink for nitrogen oxides. However, recent field studies have shown that the yield of nitryl chloride, ClNO2, from N2O5 uptake is significant in many locations. Because ClNO2 photolyzes subsequent to its nighttime production to recycle NO2 and produce atomic chlorine, a potent oxidant, the impact of heterogeneous N2O5 uptake and the role of ClNO2 on the scale distribution of oxidants need to be re-assessed. Here we present global simulations using the chemistry-climate model CAM-Chem, including a state of the art halogen chemistry scheme and different assumptions for the magnitude and spatial distribution of ClNO2 yields from N2O5. The model shows a significant effect of ClNO2 production on tropospheric ozone, hydroxyl radical and peroxyacyl nitrates (PAN) during northern hemisphere late winter and early spring. Simulations are compared to observations from recent field campaigns, including ClNO2 and N2O5 from the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) study on the NSF / NCAR C-130 aircraft on the U.S. East Coast in February and March of 2015.

  8. Evaluation and Model of Performance of A Tubular Solid Oxide Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    JIA Jun-xi; SHEN Sheng-qiang

    2005-01-01

    A simulation model was developed to analyze the steady state and transient operation of a tubular solid oxide fuel cell. The model covers both the electrochemical and the heat transfer models. The electrochemical model deals with the Nernst potential, ohmic polarization, activation polarization, and concentration polarization, while the heat transfer model concerns the heat transfer by conduction, convection and radiation. The numerical results show that the ohmic loss is the dominant one among the three polarizations in a cathode-supported solid oxide fuel cell and in the middle part of a solid oxide fuel cell the temperature is higher than those at both the ends. When the inlet temperature and the flow rates of the fuel and the oxidant are kept constantly, the temperature of the solid structure of the cell will increase due to the increase of power output of the cell from the initial state to the new one.

  9. 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.

  10. New experimental evidence and modeling study of the ethylbenzene oxidation

    OpenAIRE

    Husson, Benoit; Ferrari, Maude; Herbinet, Olivier; Sayeed Ahmed, Syed; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

    2013-01-01

    A study of the oxidation of ethylbenzene has been performed in a jet-stirred reactor (JSR) at quasi-atmospheric pressure (800 Torr), at temperatures ranging 750-1100 K, at a mean residence time of 2 s and at three equivalence ratios ϕ (0.25, 1, and 2). Reactants and 25 reaction products were analyzed online by gas chromatography after sampling in the outlet gas. A new mechanism for the oxidation of ethylbenzene was proposed whose predictions were in satisfactory agreement with the measured sp...

  11. Hydrogen production by partial oxidative gasification of biomass and its model compounds in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Hui; Lu, Youjun; Guo, Liejin; Cao, Changqing; Zhang, Ximin [State Key Laboratory of Multiphase Flow in Power Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2010-04-15

    Partial oxidative gasification in supercritical water is a new technology for hydrogen production from biomass. Firstly in this paper, supercritical water partial oxidative gasification process was analyzed from the perspective of theory and chemical equilibrium gaseous product was calculated using the thermodynamic model. Secondly, the influence of oxidant equivalent ratio on partial oxidative gasification of model compounds (glucose, lignin) and real biomass (corn cob) in supercritical water was investigated in a fluidized bed system. Experimental results show that oxidant can improve the gasification efficiency, and an appropriate addition of oxidant can improve the yield of hydrogen in certain reaction condition. When ER equaled 0.4, the gasification efficiency of lignin was 3.1 times of that without oxidant. When ER equaled 0.1, the yield of hydrogen from lignin increased by 25.8% compared with that without oxidant. Thirdly, the effects of operation parameters including temperature, pressure, concentration, and flow rate of feedstock on the gasification were investigated. The optimal operation parameters for supercritical water partial oxidative gasification were obtained. (author)

  12. 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.

  13. Arsenate and phosphate adsorption in relation to oxides composition in soils: LCD modeling.

    Science.gov (United States)

    Cui, Yanshan; Weng, Liping

    2013-07-01

    The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

  14. Empirical Modeling of Iron Oxide Dissolution in Sulphuric and Hydrochloric Acid

    Science.gov (United States)

    Hemmelmann, Jan C.; Xu, Hao; Krumm, Wolfgang

    2013-10-01

    A new approach is presented to an empirical modeling of chemical pickling processes, based on the activation energy of oxide dissolution in hydrochloric acid (HCl) and sulfuric acid (H2SO4). The model allows us to calculate pickling times as a function of definite parameters. The main oxide layers on hot-rolled materials are magnetite (Fe3O4), hematite (Fe2O3), and wustite (FeO). On the laboratory scale, the activation energy of each oxide has been determined. FeO is a metastable oxide and has been produced based on magnetite powder in a H2/H2O atmosphere. The oxide powders used for the experimental procedure have been analyzed by X-ray powder diffraction to insure the proper stoichiometry and composition. The model allows us to calculate the time of oxide dissolution based on the parameters temperature, acid concentration, and the composition of the oxide layer. Calculated values are verified by surface potential measurement on industrial oxide layers. The hot-rolled material used for verification is low carbon steel. A comparison between calculated pickling times and experimental data will be presented.

  15. 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...

  16. Modeling of autoignition and NO sensitization for the oxidation of IC engine surrogate fuels

    CERN Document Server

    Anderlohr, Jörg; Da Cruz, A Pires; Battin-Leclerc, Frédérique; 10.1016/j.combustflame.2008.09.009

    2009-01-01

    This paper presents an approch for modeling with one single kinetic mechanism the chemistry of the autoignition and combustion processes inside an internal combustion engine, as well as the chemical kinetics governing the post-oxidation of unburned hydrocarbons in engine exhaust gases. Therefore a new kinetic model was developed, valid over a wide range of temperatures including the negative temperature coefficient regime. The model simulates the autoignition and the oxidation of engine surrogate fuels composed of n-heptane, iso-octane and toluene, which are sensitized by the presence of nitric oxides. The new model was obtained from previously published mechanisms for the oxidation of alkanes and toluene where the coupling reactions describing interactions between hydrocarbons and NOx were added. The mechanism was validated against a wide range of experimental data obtained in jet-stirred reactors, rapid compression machines, shock tubes and homogenous charge compression ignition engines. Flow rate and sensi...

  17. Metal oxide surge arrester model with active V-I characteristics; Sanka aenkei hiraiki dotokusei model

    Energy Technology Data Exchange (ETDEWEB)

    Hagiwara, T.; Funabashi, T.; Watanabe, H.; Takeuchi, N. [Meidensha Corporation, Tokyo (Japan); Ueda, T. [Chubu Electric Power Co. Inc., Nagoya (Japan)

    1996-11-20

    Generally a model of Metal Oxide Surge Arrester (MOSA) for numerical analysis uses a non-linear resistance. But actual Voltage-Current (V-I) characteristics of MOSA have hysteresis loop in time domain like i-{Phi} characteristic of a transformer and frequency dependency. The authors have investigated relation between the actual V-I hysteresis characteristics obtained by some current waveforms and static V-I characteristics. From the voltage difference between above two characteristics, an equation was derived and a new model of MOSA was developed. This model consists of a non-linear resistance representing fundamental V-I characteristic, a linear inductance and voltage source which depends on the absorbed energy. The calculated results by the proposed model are compared with measurement results by using the waveform of standard impulse current, steep front current and oscillated current. And the accuracy of the model has been confirmed to be satisfactory. The model is expected to be useful to investigate insulation coordination of power systems. 11 refs., 11 figs., 2 tabs.

  18. A model for thermal oxidation of Si and SiC including material expansion

    Energy Technology Data Exchange (ETDEWEB)

    Christen, T., E-mail: thomas.christen@ch.abb.com; Ioannidis, A. [ABB Corporate Research, Segelhofstrasse 1K, CH-5405 Baden (Switzerland); Winkelmann, C. [ETH Zürich, Seminar for Applied Mathematics, Rämistrasse 101, CH-8092 Zürich (Switzerland)

    2015-02-28

    A model based on drift-diffusion-reaction kinetics for Si and SiC oxidation is discussed, which takes the material expansion into account with an additional convection term. The associated velocity field is determined self-consistently from the local reaction rate. The approach allows a calculation of the densities of volatile species in an nm-resolution at the oxidation front. The model is illustrated with simulation results for the growth and impurity redistribution during Si oxidation and for carbon and silicon emission during SiC oxidation. The approach can be useful for the prediction of Si and/or C interstitial distribution, which is particularly relevant for the quality of metal-oxide-semiconductor electronic devices.

  19. 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.

  20. Evaluation of occasional nonresponse of a washed cod mince model to hemoglobin (Hb)-mediated oxidation.

    Science.gov (United States)

    Sannaveerappa, Thippeswamy; Sandberg, Ann-Sofie; Undeland, Ingrid

    2007-05-30

    An emerging model to test antioxidants for application in seafoods is washed cod mince fortified with hemoglobin (Hb) as a catalyst. This system has been used to test the antioxidative activity of certain muscle extracts and some pure compounds such as BHA, BHT, TBHQ, and propyl gallate during ice storage. However, the washed cod mince model has occasionally been resistant to Hb-mediated oxidation. This has been in cases when the moisture of the model has been minimized by washes at the protein isoelectric point (pH approximately 5.5) to allow for large additions of potentially antioxidative solutions. In this paper, noncontrollable and controllable factors for this intriguing occasional oxidation resistance were studied. Compositional analyses (lipid content, alpha-tocopherol, and lipid hydroperoxides) and structural analysis of a "normal" oxidizing model and a stable model were done to identify any differences among them. Some controllable factors related to the model preparation that were studied included different washing pH values (5.5-6.6), Hb concentrations (7.2 and 13.5 microM), final model moisture contents (75, 81, and 90%), and light exposure during ice storage (0 h, 3-4 h, or 24 h of light/day). Results revealed a 2-fold higher alpha-tocopherol content in the stable model than in the oxidizing model. Electron microscopy images showed a more and less disrupted myofibrillar structure in the stable and the oxidizing cod model, respectively. This indicated that "cold setting" (i.e., pre-gelation) of the stable model may have occurred and prevented Hb from diffusing freely in the model. Controllable factors that reduced lipid oxidation in the models were less Hb and lower moisture. PMID:17461593

  1. 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......-electrolyte interface. Lack of atomic-level information about the interface has limited the fundamental understanding, which further limits the opportunity for optimization. The atomic structure of the interface is affected by electrode potential, chemical potential of oxygen ions, temperature and gas pressures. Here...... we present a scheme to determine the metal-oxide interface structure at a given set of these environmental parameters based on quantum chemical calculations. As an illustration we determine the structure of a Ni-YSZ anode as a function of electrode potential at 0 and 1000 K. We further describe how...

  2. 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.

  3. Influence of Heterogeneous OH Oxidation on the Evaporation Behavior and Composition of a Model Organic Aerosol

    Science.gov (United States)

    Kolesar, K. R.; Cappa, C. D.; Wilson, K. R.

    2011-12-01

    Heterogeneously oxidized squalane particles are used here as a model system to investigate the interplay between chemical composition and particle volatility. Reaction of squalane particles by OH radicals leads to the production of oxygenated products. Here we use the vacuum ultra-violet Aerosol Mass Spectrometer (VUV-AMS) at beamline 9.0.2 at the Advanced Light Source to monitor the evolution of specific oxidation products that result from increasing OH exposures, and how the composition changes as the oxidized particles evaporate. The soft ionization in the VUV-AMS allows us to uniquely track the parent squalane molecule and the various oxidation products over multiple generations of oxidation. Compositional changes of the oxidized particles resulting from evaporation have been measured in three sets of laboratory experiments. In the first set, a thermodenuder at varying temperatures was used to induce evaporation of particles at a fixed OH exposure. Second, the OH exposure was varied along with temperature to create a cross-sectional observation of particle composition at 50% mass fraction remaining for ten different oxidation levels. The combination of these two experiments provides information as to the compositional changes that occur during evaporation due to heating. In the third set of experiments, VUV-AMS spectra of oxidized squalane particles following dilution-induced evaporation were measured for comparison with the thermodenuder experiments. These experiments provide insights into the relationships between particle oxidation, composition and evaporation kinetics.

  4. 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.

  5. 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...

  6. 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). PMID:27384012

  7. Increased pulmonary arteriolar tone associated with lung oxidative stress and nitric oxide in a mouse model of Alzheimer's disease.

    Science.gov (United States)

    Roberts, Andrew M; Jagadapillai, Rekha; Vaishnav, Radhika A; Friedland, Robert P; Drinovac, Robert; Lin, Xingyu; Gozal, Evelyne

    2016-09-01

    Vascular dysfunction and decreased cerebral blood flow are linked to Alzheimer's disease (AD). Loss of endothelial nitric oxide (NO) and oxidative stress in human cerebrovascular endothelium increase expression of amyloid precursor protein (APP) and enhance production of the Aβ peptide, suggesting that loss of endothelial NO contributes to AD pathology. We hypothesize that decreased systemic NO bioavailability in AD may also impact lung microcirculation and induce pulmonary endothelial dysfunction. The acute effect of NO synthase (NOS) inhibition on pulmonary arteriolar tone was assessed in a transgenic mouse model (TgAD) of AD (C57BL/6-Tg(Thy1-APPSwDutIowa)BWevn/Mmjax) and age-matched wild-type controls (C57BL/6J). Arteriolar diameters were measured before and after the administration of the NOS inhibitor, L-NAME Lung superoxide formation (DHE) and formation of nitrotyrosine (3-NT) were assessed as indicators of oxidative stress, inducible NOS (iNOS) and tumor necrosis factor alpha (TNF-α) expression as indicators of inflammation. Administration of L-NAME caused either significant pulmonary arteriolar constriction or no change from baseline tone in wild-type (WT) mice, and significant arteriolar dilation in TgAD mice. DHE, 3-NT, TNF-α, and iNOS expression were higher in TgAD lung tissue, compared to WT mice. These data suggest L-NAME could induce increased pulmonary arteriolar tone in WT mice from loss of bioavailable NO In contrast, NOS inhibition with L-NAME had a vasodilator effect in TgAD mice, potentially caused by decreased reactive nitrogen species formation, while significant oxidative stress and inflammation were present. We conclude that AD may increase pulmonary microvascular tone as a result of loss of bioavailable NO and increased oxidative stress. Our findings suggest that AD may have systemic microvascular implications beyond central neural control mechanisms.

  8. Nitric oxide synthase and nitric oxide alterations in chronically stressed rats: a model for nitric oxide in major depressive disorder.

    Science.gov (United States)

    Gao, Shang-Feng; Lu, Yun-Rong; Shi, Li-Gen; Wu, Xue-Yan; Sun, Bo; Fu, Xin-Yan; Luo, Jian-Hong; Bao, Ai-Min

    2014-09-01

    Nitric oxide (NO) and NO synthase-1 (NOS1) are involved in the stress response and in depression. We compared NOS-NO alterations in rats exposed to chronic unpredictable stress (CUS) with alterations in major depressive disorder (MDD) in humans. In the hypothalamus of male CUS rats we determined NOS activity, and in the paraventricular nucleus (PVN) we determined NOS1-immunoreactive (ir) cell densities and co-localization of NOS1 with stress-related neuropeptides corticotropin-releasing hormone (CRH), vasopressin (AVP) or oxytocin (OXT). We measured plasma NO levels and cortisol in male medicine-naïve MDD patients and plasma NO and corticosterone (CORT) in CUS rats. In the CUS rat total NOS activity in the hypothalamus (P=0.018) and NOS1-ir cell density in the PVN were both significantly decreased (P=0.018), while NOS1 staining was mainly expressed in OXT-ir neurons in this nucleus. Interestingly, plasma NO levels were significantly increased both in male CUS rats (P=0.001) and in male MDD patients (Pdepression.

  9. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst

    Directory of Open Access Journals (Sweden)

    Muhammad Mufti Azis

    2016-03-01

    Full Text Available Exhaust after treatment for lean burn and diesel engine is a complex catalytic system that consists of a number of catalytic units. Pt/Al2O3 is often used as a model Diesel Oxidation Catalyst (DOC that plays an important role to facilitate oxidation of NO to NO2. In the present study, we proposed a detailed kinetic model of NO oxidation as well as low temperature C3H6 inhibition to simulate temperature-programmed reaction (TPR data for NO oxidation over Pt/Al2O3. A steady-state microkinetic model based on Langmuir-Hinshelwood mechanism for NO oxidation was proposed. In addition, low temperature C3H6 inhibition was proposed as a result of site blocking as well as surface nitrite consumption. The model can explain the experimental data well over the studied temperature range. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Azis, M.M., Creaser, D. (2016. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 27-33. (doi:10.9767/bcrec.11.1.403.27-33 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.403.27-33

  10. Modeling of evaporation and oxidation phenomena in plasma spraying of metal powders

    Science.gov (United States)

    Zhang, Hanwei

    Plasma spraying of metals in air is usually accompanied by evaporation and oxidation of the sprayed material. Optimization of the spraying process must ensure that the particles are fully molten during their short residence time in the plasma jet and prior to hitting the substrate, but not overheated to minimize evaporation losses. In atmospheric plasma spraying (ASP), it is also clearly desirable to be able to control the extent of oxide formation. The objective of this work to develop an overall mathematical model of the oxidization and volatilization phenomena involved in the plasma-spraying of metallic particles in air atmosphere. Four models were developed to simulate the following aspects of the atmospheric plasma spraying (APS) process: (a) the particle trajectories and the velocity and temperature profiles in an Ar-H 2 plasma jet, (b) the heat and mass transfer between particles and plasma jet, (c) the interaction between the evaporation and oxidation phenomena, and (d) the oxidation of liquid metal droplets. The resulting overall model was generated by adapting the computational fluid dynamics code FIDAP and was validated by experimental measurements carried out at the collaborating plasma laboratory of the University of Limoges. The thesis also examined the environmental implications of the oxidization and volatilization phenomena in the plasma spraying of metals. The modeling results showed that the combination of the standard k-s model of turbulence and the Boussinesq eddy-viscosity model provided a more accurate prediction of plasma gas behavior. The estimated NOx generation levels from APS were lower than the U.S.E.P.A. emission standard. Either enhanced evaporation or oxidation can occur on the surface of the metal particles and the relative extent is determined by the process parameters. Comparatively, the particle size has the greatest impact on both evaporation and oxidation. The extent of particle oxidation depends principally on gas

  11. 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.

  12. A mathematical model for the bacterial oxidation of a sulfide ore concentrate

    Energy Technology Data Exchange (ETDEWEB)

    Nagpal, S.; Dahlstrom, D. (Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemical Engineering); Oolman, T. (Radian Corp., Austin, TX (United States))

    1994-03-05

    The effect of dilution rate and feed solids concentration on the bacterial leaching of a pyrite/arsenopyrite ore concentrate was studied. A mathematical model was developed for the process based on the steady-state data collected over the range of dilution rates (20 to 110 h) and feed solids concentrations (6 to 18% w/v) studied. A modified Monod model with inhibition by arsenic was used to model bacterial ferrous ion oxidation rates. The model assumes that (1) pyrite and arsenopyrite leaching occurs solely by the action of ferric iron produced from the bacterial oxidation of ferrous iron and (2) bacterial growth rates are proportional to ferrous ion oxidation rate. The equilibrium among the various ionic species present in the leach solution that are likely to have a significant effect on the bioleach process were included in the model.

  13. Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

    Science.gov (United States)

    Zaitsevskii, Andréi; Mosyagin, Nikolai S.; Titov, Anatoly V.; Kiselev, Yuri M.

    2013-07-01

    The results of electronic structure modeling of plutonium and americium higher oxide molecules (actinide oxidation states VI through VIII) by two-component relativistic density functional theory are presented. Ground-state equilibrium molecular structures, main features of charge distributions, and energetics of AnO3, AnO4, An2On (An=Pu, Am), and PuAmOn, n = 6-8, are determined. In all cases, molecular geometries of americium and mixed plutonium-americium oxides are similar to those of the corresponding plutonium compounds, though chemical bonding in americium oxides is markedly weaker. Relatively high stability of the mixed heptoxide PuAmO7 is noticed; the Pu(VIII) and especially Am(VIII) oxides are expected to be unstable.

  14. 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.

  15. 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....

  16. 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.

  17. Analytical model of LDMOS with a single step buried oxide layer

    Science.gov (United States)

    Yuan, Song; Duan, Baoxing; Cao, Zhen; Guo, Haijun; Yang, Yintang

    2016-09-01

    In this paper, a two-dimensional analytical model is established for the Single-Step Buried Oxide SOI structure proposed by the authors. Based on the two-dimensional Poisson equation, the analytic expression of the surface electric field and potential distributions for the device is achieved. In the SBOSOI (Single-Step Buried Oxide Silicon On Insulator) structure, the buried oxide layer thickness changes stepwise along the drift region, and the electric field in the oxide layer also varies with the different buried oxide layer thickness. These variations will modulate the surface electric field distribution through the electric field modulation effects, which makes the surface electric field distribution more uniform. As a result, the breakdown voltage of the device is improved by 60% compared with the conventional SOI structure. To verify the accuracy of the analytical model, the device simulation software ISE TCAD is utilized, the analytical values are in good agreement with the simulation results by the simulation software. The results verified the established two-dimensional analytical model for SBOSOI structure is valid, and it also illustrates the breakdown voltage enhancement by the electric field modulation effect sufficiently. The established analytical models will provide the physical and mathematical basis for further analysis of the new power devices with the patterned buried oxide layer.

  18. 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...

  19. 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.

  20. Conditional Induction of Oxidative Stress in RPE: A Mouse Model of Progressive Retinal Degeneration.

    Science.gov (United States)

    Biswal, Manas R; Ildefonso, Cristhian J; Mao, Haoyu; Seo, Soo Jung; Wang, Zhaoyang; Li, Hong; Le, Yun Z; Lewin, Alfred S

    2016-01-01

    An appropriate animal model is essential to screening drugs or designing a treatment strategy for geographic atrophy. Since oxidative stress contributes to the pathological changes of the retinal pigment epithelium (RPE), we are reporting a new mouse AMD model of retinal degeneration by inducing mitochondrial oxidative stress in RPE. Sod2 the gene for manganese superoxide dismutase (MnSOD) was deleted in RPE layer using conditional knockout strategy. Fundus microscopy, SD-OCT and electroretinography were used to monitor retinal structure and function in living animals and microscopy was used to assess pathology post mortem. Tissue specific deletion of Sod2 caused elevated signs of oxidative stress, RPE dysfunction and showed some key features of AMD. Due to induction of oxidative stress, the conditional knockout mice show progressive reduction in ERG responses and thinning of outer nuclear layer (ONL) compared to non-induced littermates. PMID:26427390

  1. Anxiolytic-like effects of inhaled linalool oxide in experimental mouse anxiety models.

    Science.gov (United States)

    Souto-Maior, Flávia Negromonte; de Carvalho, Fabíola Lélis; de Morais, Liana Clébia Soares Lima; Netto, Sueli Mendonça; de Sousa, Damião Pergentino; de Almeida, Reinaldo Nóbrega

    2011-12-01

    Linalool oxide is a monoterpene that is found in some species of aromatic plants. The effects of the inhalation of linalool oxide (0.65%, 1.25%, 2.5% and 5.0% w/w) in the elevated plus-maze and light/dark box tests as animal models of anxiety were investigated in adult male mice and compared with the effects of the reference anxiolytic diazepam (0.5 and 2.0 mg/kg), administered intraperitoneally. Additionally, the effects of inhaled linalool oxide were investigated in the rotarod test. Linalool oxide significantly increased the number of visits to the open arms of the elevated plus-maze and the amount of time spent there as well as the total number of entries. In the light/dark box test, inhalation of linalool oxide led to an increase in the time spent by the mice in the brightly-lit chamber and in the number of times the animal crossed from one compartment to another. Performance on the rotarod was unaffected. Thus, inhaled linalool oxide was found to have anxiolytic properties in both animal models, without causing any motor deficit. These results suggest that inhalation of linalool oxide may be a useful means of counteracting anxiety.

  2. 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....

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

    Science.gov (United States)

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

    2015-10-01

    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.

  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. Submicro-battery effect and selective bio-oxidation model of gold-bearing arsenopyrite by Thiobacillus ferrooxidans

    Institute of Scientific and Technical Information of China (English)

    杨洪英; 杨立; 赵玉山; 陈刚; 吕久吉; 范有静

    2002-01-01

    Through the study by electronic probe it was found that many new cracks and holes appear on the surface of gold-bearing arsenopyrite crystal oxidized by Thiobacillus ferrooxidans, which are along with some directions. Then the selective bio-oxidation model of gold-bearing arsenopyrite was set up. The selective bio-oxidation resulting from the submicro-battery effect of gold/ arsenopyrite mineral pairs naturally forms in the gold-bearing arsenopyrite crystal. Thiobacillus ferrooxidans has priority to oxidize the place of gold-rich and oxidizes selectedly along with the crystal border, crystal face and crack. The bacteria oxidation process of gold-bearing arsenopyrite is divided into three stages: the first stage is the surface oxidation, the second stage is restraining oxidation and the third stage is the filament oxidation, bacteria oxidize along with cracks of arsenopyrite.

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

    International Nuclear Information System (INIS)

    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 UO2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO2, 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

  7. Model-based Interpretation of the Performance and Degradation of Reformate Fueled Solid Oxide Fuel Cells

    OpenAIRE

    Kromp, Alexander

    2013-01-01

    Solid oxide fuel cells offer great prospects for the sustainable, clean and safe conversion of various fuels into electrical energy. In this thesis, the performance-determining loss processes for the cell operation on reformate fuels are elucidated via electrochemical impedance spectroscopy. Model-based analyses reveal the electrochemical fuel oxidation mechanism, the coupling of fuel gas transport and reforming chemistry and the impact of fuel impurities on the degradation of each loss process.

  8. Effects of Laminaria japonica polysaccharides on exercise endurance and oxidative stress in forced swimming mouse model

    OpenAIRE

    Yan, Feiwei; Hao, Haitao

    2016-01-01

    Background 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...

  9. Theoretical modeling of heterogeneous catalysts based on platinum and cerium oxide

    OpenAIRE

    Bruix Fusté, Albert

    2014-01-01

    This thesis focuses on the computational study of models for platinum catalysts supported on cerium oxide (CeO2) which are of technological relevance. In these catalysts, ceria is often found acting as a non-inert support, leading to complex metal-support interactions (MSI) that modify the properties of both the oxide and the supported metal. First principles computational methods based on the Density functional Theory (DFT) have been used to study the nature of these interactions and their e...

  10. Modelling of Physical, Chemical, and Material Properties of Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jakub Kupecki

    2015-01-01

    Full Text Available This paper provides a review of modelling techniques applicable for system-level studies to account for physical, chemical, and material properties of solid oxide fuel cells. Functionality of 0D to 3D models is discussed and selected examples are given. Author provides information on typical length scales in evaluation of power systems with solid oxide fuel cells. In each section, proper examples of previous studies done in the field of 0D–3D modelling are recalled and discussed.

  11. 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.

  12. Kinetic Model of Hypophosphite Oxidation on a Nickel Electrode in D2O Solution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Kinetic model of hypophosphite oxidation on a nickel electrode was studied in D2Osolution in order to reach a better understanding of the oxidation mechanism. In the model the electrooxidation of hypophosphite undergo a H abstraction of hypophosphite from the P-H bond to form the phosphorus-centered radical PHO2-, which subsequently is electrochemically reacted with water to form the final product, phosphite. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The process of hypophosphite electrooxidation could be well simulated by this model

  13. Oxidatively Robust Monophenolate-Copper(II) Complexes as Potential Models of Galactose Oxidation

    NARCIS (Netherlands)

    Koten, G. van; Klein Gebbink, R.J.M.; Watanabe, M.; Pratt, R.C.; Stack, D.P.

    2003-01-01

    Cupric complexes of a novel phenanthroline-phenolate ligand have strongly distorted coordination geometries and electrochemical properties conducive to modeling the spectroscopy and reactivity of the enzyme galactose oxidase.

  14. Application of the Generic Modeling Template Approach to Unsaturated Fatty Acid Oxidation and Crystallization Systems

    DEFF Research Database (Denmark)

    Fedorova, Marina; Papadakis, Emmanouil; Meisler, Kresten Troelstrup;

    2014-01-01

    for following the modelling workflow steps, guidance through the steps , as well as providing additional information and comments. The application of the tool is highlighted with two case studies: oxidation of unsaturated acid with hydrogen peroxide and modeling of a crystal lization operation...... for the paracetamol-ethanol system....

  15. Wet oxidation lumped kinetic model for wastewater organic burden biodegradability prediction.

    Science.gov (United States)

    Verenich, Svetlana; Kallas, Juha

    2002-08-01

    In many cases, treatment of wastewaters requires a combination of processes that very often includes biological treatment. Wet oxidation (WO) in combination with biotreatment has been successfully used for the treatment of refractory wastes. Therefore, information about the biodegradability of wastewater solutes and particulates after wet oxidation is very important. The present work proposes a model that can describe the oxidation process via organic concentration characteristics such as chemical oxygen demand (COD), biochemical oxygen demand (BOD), and immediately available BOD (IA BOD) and so can allow the prediction of biodegradability (i.e., BOD/COD ratio). The reaction mechanism includes the destruction of nonbiodegradable substances bytwo pathways: oxidation to carbon dioxide and water and oxidation to larger biodegradable compounds with their further degradation to smaller ones measured via IA BOD. The destruction of small biodegradable compounds to end products is also included in the model. The experiments were performed at different temperatures (170-200 degrees C) and partial oxygen pressures (0.5-1.5 MPa) in a batch stainless steel high-pressure autoclave. The model of concentrated thermomechanical pulp circulation water was selected for the experiments. The proposed model correlates with the experimental data well and it is compared with other WO models in the literature. PMID:12188362

  16. Modeling of methane oxidation in landfill cover soil using an artificial neural network.

    Science.gov (United States)

    Abushammala, Mohammed F M; Basri, Noor Ezlin Ahmad; Elfithri, Rahmah; Younes, Mohammad K; Irwan, Dani

    2014-02-01

    Knowing the fraction of methane (CH4) oxidized in landfill cover soils is an important step in estimating the total CH4 emissions from any landfill. Predicting CH4 oxidation in landfill cover soils is a difficult task because it is controlled by a number of biological and environmental factors. This study proposes an artificial neural network (ANN) approach using feedforward backpropagation to predict CH4 oxidation in landfill cover soil in relation to air temperature, soil moisture content, oxygen (O2) concentration at a depth of 10 cm in cover soil, and CH4 concentration at the bottom of cover soil. The optimum ANN model giving the lowest mean square error (MSE) was configured from three layers, with 12 and 9 neurons at the first and the second hidden layers, respectively, log-sigmoid (logsig) transfer function at the hidden and output layers, and the Levenberg-Marquardt training algorithm. This study revealed that the ANN oxidation model can predict CH4 oxidation with a MSE of 0.0082, a coefficient of determination (R2) between the measured and predicted outputs of up to 0.937, and a model efficiency (E) of 0.8978. To conclude, further developments of the proposed ANN model are required to generalize and apply the model to other landfills with different cover soil properties.

  17. Modeling and Structural Optimization of Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Panagakos, Grigorios

    for dealing with this problem. On the one hand, we attempt to perform optimization of a Solid Oxide Fuel Cell in the macro scale. Focusing on the anode interconnect, we wish to come up with an optimum interconnect design. This can be achieved in principal, since the interconnect needs to satisfy two major...... requirements. On the one hand, it needs to secure the intake of fuel into the cell, fact that would require an as low hydraulic resistance as possible, i.e. ideally an open channel and on the other hand to exhibit an as high as possible electronic conductance, which in the ideal case would mean an area blocked...... approaches and this is one of the first attempts to apply this combination of set of tools to fuel cells. Describing in a nutshell the methodology followed, we use Comsol's ability to create Matlab scripts which incorporate the desired physics of the problem (Partial Differential Equations, treating...

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    A simulation package for the impedance response of SOFC anodes is presented here. The model couples the gas transport in gas channels and within a porous electrode with the electrochemical kinetics. The gas phase mass transport is modeled using mass conservation equations. A transmission line model...... (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...

  19. 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 < 0.0008), decreased plasma antioxidant capacity (3.17 ± 1.35 μM versus 7.74 ± 4.45 μM, p < 0.0001) and plasma total thiol (SH groups) (0.21 ± 0.07 μM versus 0.45 ± 0.41 μM, p < 0.0042) in comparison to controls. Based on the oxidative parameters, two groups were identified by PCA methods. One category is workers with the risk of oxidative stress and second group is subjects with probable risk of oxidative stress induction. ANN methods can predict oxidative-risk category for assessment of toxicity induction in 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.

  20. Effect of glutathione on brain nitric oxide levels in an experimental epilepsy mouse model

    Institute of Scientific and Technical Information of China (English)

    Aylin Akcali; Sadrettin Pence; Naciye Kurtul; Mehmet Bosnak; Munife Neyal

    2009-01-01

    BACKGROUND: Oxidative stress plays an important role in the pathophysiology of epilepsy. Glutathione, known as one of the compounds of antioxidant defense, has been shown to inhibit convulsions. Nitric oxide has a proconvulsant effect on a pentylenetetrazole-induced animal model. OBJECTIVE: To evaluate the effects of glutathione administration on nitric oxide levels in brain regions of convulsive and kindling pentylenetetrazole-induced seizure models. DESIGN, TIME, AND SETTING: A randomized, controlled, animal experiment. The study was performed at the Department of Physiology, Gaziantep University and Department of Chemistry-Biochemistry, Kahramamaras Sutcu Imam University in 2006.MATERIALS: Pentylenetetrazole and glutathione were purchased from Sigma, USA. METHODS: A total of 80 mice were assigned to 8 groups (n=10): normal control, saline control (1 mL normal saline), convulsive pentylenetetrazole (single intraperitoneal administration of pentylenetetrazole, 60 mg/kg), convulsive pentylenetrazole plus glutathione (single administration of 60 mg/kg pentylenetetrazole and 200 mg/kg glutathione), five-dose glutathione (intraperitoneal injection of 200 mg/kg glutathione respectively at 1, 3, 5, 7, and 10 days), single-dose glutathione (single administration of 200 mg/kg glutathione), pentylenetetrazole kindling (intraperitoneal administration of pentylenetetrazole of 40 mg/kg at 1, 3, 5, 7, and 10 days), and pentylenetetrazole kindling plus glutathione group (intraperitoneal injection of 40 mg/kg pentylenetetrazole and 200 mg/kg glutathione respectively at 1, 3, 5, 7, and 10 days). MAIN OUTCOME MEASURES: All mice were sacrificed 1 hour after the last administration. Brain nitric oxide levels were determined by spectrophotometry. RESULTS: There were no significant differences in nitric oxide levels between the normal control, saline control, five-dose glutathione, and single-dose glutathione groups (P>0.05). Nitric oxide levels in the cerebral hemisphere and

  1. Modeling Study of Cyclic Oxidation Behavior of NiAl and NiCr Alloys

    Science.gov (United States)

    Peng, X. J.; Chen, K. Y.; Liu, R.; Liang, M.

    2014-12-01

    The cyclic oxidation behavior of four high-temperature alloys (two NiAl alloys and two NiCr alloy) is studied utilizing an existing micromechanics-based model, in which Al2O3 and Cr2O3 are formed on the alloys as protective layers. For each alloy, the model parameters are determined based on one `complete' experimental curve of weight change, which is obtained under a high-temperature cyclic oxidation test where the weight change experiences a maximum value and then drops down to a zero point. The model is first tested on two metals which have experimental data available for comparison. It is found that the model parameter, oxide crack density exponent, can be assumed constant within a range of high temperature for each metal, thus with the `complete' experimental curve of weight change, the model can predict the oxidation behavior of the metal at different temperatures. The determination of model parameters, accuracy, and limitations of the model for NiAl and NiCr alloys is analyzed and discussed.

  2. Analytical model of LDMOS with a double step buried oxide layer

    Science.gov (United States)

    Yuan, Song; Duan, Baoxing; Cao, Zhen; Guo, Haijun; Yang, Yintang

    2016-09-01

    In this paper, a two-dimensional analytical model is established for the Buried Oxide Double Step Silicon On Insulator structure proposed by the authors. Based on the two-dimensional Poisson equation, the analytic expressions of the surface electric field and potential distributions for the device are achieved. In the BODS (Buried Oxide Double Step Silicon On Insulator) structure, the buried oxide layer thickness changes stepwise along the drift region, and the positive charge in the drift region can be accumulated at the corner of the step. These accumulated charge function as the space charge in the depleted drift region. At the same time, the electric field in the oxide layer also varies with the different drift region thickness. These variations especially the accumulated charge will modulate the surface electric field distribution through the electric field modulation effects, which makes the surface electric field distribution more uniform. As a result, the breakdown voltage of the device is improved by 30% compared with the conventional SOI structure. To verify the accuracy of the analytical model, the device simulation software ISE TCAD is utilized, the analytical values are in good agreement with the simulation results by the simulation software. That means the established two-dimensional analytical model for BODS structure is valid, and it also illustrates the breakdown voltage enhancement by the electric field modulation effect sufficiently. The established analytical models will provide the physical and mathematical basis for further analysis of the new power devices with the patterned buried oxide layer.

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

    International Nuclear Information System (INIS)

    Highlights: ► A 2D model is developed for solid oxide fuel cells (SOFCs). ► CH4 reforming by CO2 (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 CO2 and CH4 mixture. The electrochemical oxidations of both CO and H2 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 CH4/CO2 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 CO2/CH4 mixture is comparable to SOFC running on CH4/H2O 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 CH4/CO2 mixtures

  4. A functional group oxidation model (FGOM for SOA formation and aging

    Directory of Open Access Journals (Sweden)

    X. Zhang

    2013-06-01

    Full Text Available Secondary organic aerosol (SOA formation from a volatile organic compound (VOC involves multiple generations of oxidation that include functionalization and fragmentation of the parent carbon backbone and likely particle-phase oxidation and/or accretion reactions. Despite the typical complexity of the detailed molecular mechanism of SOA formation and aging, a relatively small number of functional groups characterize the oxidized molecules that constitute SOA. Given the carbon number and set of functional groups, the volatility of the molecule can be estimated. We present here a functional group oxidation model (FGOM that represents the process of SOA formation and aging. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data: total organic aerosol concentration, and O : C and H : C atomic ratios. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation. An analysis of SOA formation from the high- and low-NOx photooxidation of four C12 alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane using the FGOM is presented, and comparison with the statistical oxidation model (SOM of Cappa et al. (2013 is discussed.

  5. A many-body potential approach to modelling the thermomechanical properties of actinide oxides.

    Science.gov (United States)

    Cooper, M W D; Rushton, M J D; Grimes, R W

    2014-03-12

    A many-body potential model for the description of actinide oxide systems, which is robust at high temperatures, is reported for the first time. The embedded atom method is used to describe many-body interactions ensuring good reproduction of a range of thermophysical properties (lattice parameter, bulk modulus, enthalpy and specific heat) between 300 and 3000 K for AmO2, CeO2, CmO2, NpO2, ThO2, PuO2 and UO2. Additionally, the model predicts a melting point for UO2 between 3000 and 3100 K, in close agreement with experiment. Oxygen-oxygen interactions are fixed across the actinide oxide series because it facilitates the modelling of oxide solid solutions. The new potential is also used to predict the energies of Schottky and Frenkel pair disorder processes.

  6. Effects of glucocorticoid dexamethasone on serum nitric oxide synthase activity and nitric oxide levels in a rat model of lung disease-induced brain injury

    Institute of Scientific and Technical Information of China (English)

    Huajun Li; Ligang Jiang; Meng Xia; Haiping Li; Fanhua Meng; Wei Li; Lifeng Liu; Zhaohui Wang

    2011-01-01

    In this study, we investigated the effects of dexamethasone, pertussis toxin (a Gi protein inhibitor), and actinomycin (a transcription inhibitor) on serum nitric oxide synthase activity and nitric oxide content in a rat model of lung disease-induced brain injury. High-dose dexamethasone (13 mg/kg) and dexamethasone + actinomycin reduced lung water content, increased serum nitric oxide synthase activity and nitric oxide content, diminished inflammatory cell infiltration in pulmonary alveolar interstitium, attenuated meningeal vascular hyperemia, reduced glial cell infiltration, and decreased cerebral edema. These results demonstrate that high-dose glucocorticoid treatment can reduce the severity of lung disease-induced brain injury by increasing nitric oxide synthase activity and nitric oxide levels.

  7. Performance model for large area solid oxide fuel cells

    Science.gov (United States)

    Klotz, Dino; Schmidt, Jan Philipp; Weber, André; Ivers-Tiffée, Ellen

    2014-08-01

    A parameter set obtained from a 1 cm2 size electrode cell is used to develop and calibrate a one-dimensional spatially resolved model. It is demonstrated that this performance model precalculates the evolving operating parameters along the gas channel of a large-sized cell. Input parameters are: (i) number of discretization elements N, accounting for anodic gas conversion, (ii) anodic gas flow rate and composition and (iv) operating voltage. The model calculations based on data from the 1 cm2 cell are scaled to be equivalent to a larger cell with 16 cm2 electrode size which is used to validate the performance model. The current/voltage characteristics can be predicted very accurately, even when anodic gas flow rates vary by as much as a factor of four. The performance model presented herein simulates the total overvoltage and does so in a broad range of operation conditions. This is done with an accuracy of the simulated current better than 6.1% for UOP = 0.85 V, 3.8% for UOP = 0.8 V and 3.7% for UOP = 0.75 V. It is hoped that these equations will form the basis of a greater model, capable of predicting all the conditions found throughout any industrial stack.

  8. Integrated modeling of nitrogen oxides formation in diesel engines

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    To account for the effects of both chemistry and flow turbulence,the present study proposes an integrated NO sub-model that combines the extended Zel'dovich mechanism and engine CFD computations to simulate the NO histories in a diesel engine.NOx sub-model parameters and pollutant formation mechanisms can be more easily investigated by solving the NOx sub-model.The new NO formation model incorporating the effects of hoth chemical kinetics and turbulent mixing was applied to simulate a diesel engine with a quiescent combustion chamber,and one with a re-entrant combustion chamber;the premise of the model being the reaction rate is mainlv determined by a kinetic timescale and a turbulent timescale.The results indicate that the predicted NO formulation from the new model agrees well with the measured data.As the utilization of fossil fuels continues to increase,the control of NOx emissions is a worldwide concern;and it is imperative to understand fully the NOx reaction processes in combustion systems.This technology has the Dotential to enhance the application of various combustion techniques used to reduce NOx emissions from practical combustion systems.

  9. Microstructural Modeling of Thermal Conductivity of High Burn-up Mixed Oxide Fuel

    International Nuclear Information System (INIS)

    Predicting the thermal conductivity of oxide fuels as a function of burn-up and temperature is fundamental to the efficient and safe operation of nuclear reactors. However, modeling the thermal conductivity of fuel is greatly complicated by the radially inhomogeneous nature of irradiated fuel in both composition and microstructure. In this work, radially and temperature-dependent models for effective thermal conductivity were developed utilizing optical micrographs of high burn-up mixed oxide fuel. The micrographs were employed to create finite element meshes with the OOF2 software. The meshes were then used to calculate the effective thermal conductivity of the microstructures using the BISON fuel performance code. The new thermal conductivity models were used to calculate thermal profiles at end of life for the fuel pellets. These results were compared to thermal conductivity models from the literature, and comparison between the new finite element-based thermal conductivity model and the Duriez-Lucuta model was favorable

  10. Evidence of amorphisation of B4C boron carbide under slow, heavy ion irradiation

    Science.gov (United States)

    Gosset, D.; Miro, S.; Doriot, S.; Victor, G.; Motte, V.

    2015-12-01

    Boron carbide is widely used either as armor-plate or neutron absorber. In both cases, a good structural stability is required. However, a few studies have shown amorphisation may occur in severe conditions. Hard impacts lead to the formation of amorphous bands. Some irradiations in electronic regime with H or He ions have also shown amorphisation of the material. Most authors however consider the structure is not drastically affected by irradiations in the ballistic regime. Here, we have irradiated at room temperature dense boron carbide pellets with Au 4 MeV ions, for which most of the damage is in the ballistic regime. This study is part of a program devoted to the behavior of boron carbide under irradiation. Raman observations have been performed after the irradiations together with transmission electron microscopy (TEM). Raman observations show a strong structural damage at moderate fluences (1014/cm2, about 0.1 dpa), in agreement with previous studies. On the other hand, TEM shows the structure remains crystalline up to 1015/cm2 then partially amorphises. The amorphisation is heterogeneous, with the formation of nanometric amorphous zones with increasing density. It then appears short range and long range disorder occurs at quite different damage levels. Further experiments are in progress aiming at studying the structural stability of boron carbide and isostructural materials (α-B, B6Si,…).

  11. Machinability Studies on Turning Al 6061alloy with 10% Reinforcement of B4C on MMC

    Directory of Open Access Journals (Sweden)

    Srivathsan A.

    2016-01-01

    Full Text Available Aluminum Boron Carbide Metal Matrix Composites (Al-MMC have revolutionized aeronautical and automobile industries, in the recent times due to their exceptional mechanical and physical properties. However it is seen that the machinability of these composites is greatly reduced by the hardness of constituent reinforcement particles. Moreover these constituent reinforcement particles serve as disadvantage by increasing tool wear accompanying undesirable depression in life of tool. This paper presents the experimental investigations on turning of Al6061 matrix metal reinforced with 10 % by weight of boron carbide (B4Cp particles - which was fabricated using Stir casting method. Fabricated samples are turned on medium duty lathe of 2kW spindle power with Polycrystalline Diamond (PCD inserts of 1500 grade at various cutting conditions by varying parameters. Hence, parameters such as power consumed by main spindle, machined surface roughness and tool wear are studied and recorded. Furthermore, study results are supported using concurring images obtained from Scanning Electron Microscopy (SEM. It is observed that surface finish and power consumed for 1500 grade insert are comparatively better at higher cutting speeds. Additionally it is observed that tool wear is strongly dependent on abrasive hard reinforcement particles.

  12. A $B_4C$-silicon target for the detection of neutrino interactions

    CERN Document Server

    Barichello, G; Daniels, D C; do Couto e Silva, E; Dumps, Ludwig; Ellis, M; Ferrère, D; Gómez-Cadenas, J J; Gössling, C; Gouanère, M; Hernando, J A; Huta, W; Jiménez, J M; Kokkonen, J; Kuznetsov, V E; Linssen, Lucie; Long, J; Lisowski, B; Lupi, A; Runólfsson, O; Schmidt, B; Soler, F J P; Steele, D; Stipcevic, M; Veltri, M; Voillat, D

    1998-01-01

    This note describes the construction of a target for neutrino interactions composed of passive boron carbide plates interleaved with silicon microstrip detectors. The target contains four layers of passive material with a total mass of 45 kg and 600 single--sided silicon microstrip detectors with a total surface of 1.14 m$^2$ distributed over five layers. It is installed in the NOMAD spectrometer at the CERN SPS neutrino beam. During the 1997 run about 8000 \

  13. Selective laser sintering of cermet mixtures Ti and B4C

    Science.gov (United States)

    Filippov, A. A.; Fomin, V. M.; Malikov, A. G.; Orishich, A. M.

    2016-10-01

    The work is dedicated to the creation of a new heterogeneous ceramic-composite materials based on boron carbide and titanium, using a laser, in order to further layer-growing 3D products from these materials. The paper discussed two methods for obtaining ceramic-composite material: laser sintering of boron carbide powder and a metal-melting the powder mixture. We study the microstructure of the samples at various energy process modes. An attempt was made to justify the applicability of the regime used for the cultivation of layered products.

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

    DEFF Research Database (Denmark)

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

    1995-01-01

    is obtained at the expense of a 20% to 30% loss of throughput over the 2-to 4-keV band. These designs lend themselves well to astrophysics missions, such as spectroscopy of the H- and He-like iron emission lines (6.4 to 7.1 keV). The technology for multilayer coating, mounting, and configuring of the flat...... of intermediate-sized telescopes of (1) the nested Kirkpatrick-Baez geometry and (2) the conical approximation to a nested Wolter-I geometry is computed. Depending on the multilayer design, the throughput was increased by a factor of 3 to 5 in a 1.5-keV wide band, or by 30% to 100% in a 3-keV-wide band. This gain...

  15. 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 ref...

  16. Modelling and engineering of stress based controlled oxidation effects for silicon nanostructure patterning

    Science.gov (United States)

    Han, Xiang-Lei; Larrieu, Guilhem; Krzeminski, Christophe

    2013-12-01

    Silicon nanostructure patterning with tight geometry control is an important challenge at the bottom level. In that context, stress based controlled oxidation appears to be an efficient tool for precise nanofabrication. Here, we investigate the stress-retarded oxidation phenomenon in various silicon nanostructures (nanobeams, nanorings and nanowires) at both the experimental and the theoretical levels. Different silicon nanostructures have been fabricated by a top-down approach. Complex dependence of the stress build-up on the nano-object’s dimension, shape and size has been demonstrated experimentally and physically explained by modelling. For the oxidation of a two-dimensional nanostructure (nanobeam), relative independence to size effects has been observed. On the other hand, radial stress increase with geometry downscaling of a one-dimensional nanostructure (nanowire) has been carefully emphasized. The study of shape engineering by retarded oxidation effects for vertical silicon nanowires is finally discussed.

  17. Modelling and engineering of stress based controlled oxidation effects for silicon nanostructure patterning

    International Nuclear Information System (INIS)

    Silicon nanostructure patterning with tight geometry control is an important challenge at the bottom level. In that context, stress based controlled oxidation appears to be an efficient tool for precise nanofabrication. Here, we investigate the stress-retarded oxidation phenomenon in various silicon nanostructures (nanobeams, nanorings and nanowires) at both the experimental and the theoretical levels. Different silicon nanostructures have been fabricated by a top-down approach. Complex dependence of the stress build-up on the nano-object’s dimension, shape and size has been demonstrated experimentally and physically explained by modelling. For the oxidation of a two-dimensional nanostructure (nanobeam), relative independence to size effects has been observed. On the other hand, radial stress increase with geometry downscaling of a one-dimensional nanostructure (nanowire) has been carefully emphasized. The study of shape engineering by retarded oxidation effects for vertical silicon nanowires is finally discussed. (paper)

  18. Protective effects of MCI-186 on oxidative damage in a cell model of Alzheimer's disease

    Institute of Scientific and Technical Information of China (English)

    Ming Yu; Shujuan Li; Wenhui Leng; Han Chen; Yingquan Wu; Lirong Yan

    2010-01-01

    Oxidative stress has an important role in the development of Alzheimer's disease(AD).Beta amyloid protein 25 35(Aβ25-35)can generate oxygen free radicals,and MCI-186(3-methyl-1-phenyl-2-pyrazolin-5-one,edaravone)can specifically eliminate hydroxyl radicals.The present study introduced Aβ25-35 into PC12 cells to establish a cell model of AD,and investigated the neuroprotective effects of MCI-186 on AD.Results showed that MCI-186 had a positive effect on the prevention and treatment of AD by inhibiting protein oxidative products,advanced glycation end products,lipid oxidative end products and DNA oxidative damage in PC12 cells induced by Aβ25-35.

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

    International Nuclear Information System (INIS)

    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 PuO2 by water to produce PuO2+x, an oxide that can release Pu(V) to solution. Kinetic relationships between formation of PuO2+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

  20. An improved model to evaluate the oxidation kinetics of uranium dioxide during dry storage

    International Nuclear Information System (INIS)

    During dry air storage, the oxidation of the spent fuel in case of cladding and container failure (accidental scenario) could be detrimental for further handling of the spent fuel rod and for the safety of the facilities. Recently, the phase transition sequence during the first step of parabolic oxidation kinetic has been challenged again and two well-distinguished intermediate products, U4O9 and U3O7 have been identified. Moreover, these observations have shown that the three phases (UO2, U4O9 and U3O7) occur together. Starting from a previous model of grain oxidation based on finite difference approach, a new model, describing the parabolic oxidation kinetic, has been developed based on the oxygen atom diffusion. This model allows in one hand to take into account the occurrence of the three phases and in another hand to describe accurately the plateau behaviour. A comparison between the model and literature data obtained on non-irradiated powders has been carried out and shows that this model can describe the weight gain evolution as a function of time for different temperatures. The diffusion coefficients of oxygen in the two phases (U4O9 and U3O7) were obtained by fitting the model results to experimental data. The comparison with the values given in literature is quite good

  1. Modelling of cladding oxidation by air under severe accident conditions with the MAAP 4 code

    International Nuclear Information System (INIS)

    In a nuclear power plant, air ingress into the vessel is a potential risk in some low probable situations of severe accidents. Air is a highly oxidizing atmosphere that can lead to an enhanced core oxidation and degradation affecting the release of FP. This is particularly true speaking about ruthenium release, which can be significantly increased in the presence of air. This is a key issue due to the high radio-toxicity of ruthenium and its ability to form highly volatile oxides. The oxygen affinity is decreasing in priority from the Zircaloy cladding, to 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. As a first step, a phenomenological study has been carried out to characterize nitriding of the Zircaloy claddings. In summary, nitriding occurs preferentially when the oxygen has been consumed locally or in case of total oxygen starvation and when the cladding was slightly pre-oxidized. Just like oxidation, nitriding can be modeled in a simplified form as a cladding weight gain in terms of thickness. The model implemented in MAAP takes this into account as well as re-oxidation of the nitrides, in the case where oxygen is available again (especially during a reflood). Several correlations were thus integrated and a new one, called “KIT-EDF”, was developed, based on KIT separate-effect tests. The model has been implemented and validated against QUENCH-16 and QUENCH-10 experiments, studying the oxidation in air atmosphere of an assembly pre-oxidized in steam and finally quenched with water. The simulations give encouraging results since the modeling of nitriding effects has increased hydrogen production during reflood, as experimentally observed. The results of this study lead us to identify a number of perspectives for the future, namely taking into account the changes in the structure of the oxide layer during a

  2. A General Mechanistic Model of Solid Oxide Fuel Cells

    Institute of Scientific and Technical Information of China (English)

    SHI Yixiang; CAI Ningsheng

    2006-01-01

    A comprehensive model considering all forms of polarization was developed. The model considers the intricate interdependency among the electrode microstructure, the transport phenomena, and the electrochemical processes. The active three-phase boundary surface was expressed as a function of electrode microstructure parameters (porosity, coordination number, contact angle, etc.). The exchange current densities used in the simulation were obtained by fitting a general formulation to the polarization curves proposed as a function of cell temperature and oxygen partial pressure. A validation study shows good agreement with published experimental data. Distributions of overpotentials, gas component partial pressures, and electronic/ionic current densities have been calculated. The effects of a porous electrode structure and of various operation conditions on cell performance were also predicted. The mechanistic model proposed can be used to interpret experimental observations and optimize cell performance by incorporating reliable experimental data.

  3. 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.

  4. 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.

  5. 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...

  6. Physical model for trap-assisted inelastic tunneling in metal-oxide-semiconductor structures

    Science.gov (United States)

    Jiménez-Molinos, F.; Palma, A.; Gámiz, F.; Banqueri, J.; López-Villanueva, J. A.

    2001-10-01

    A physical model for trap-assisted inelastic tunnel current through potential barriers in semiconductor structures has been developed. The model is based on the theory of multiphonon transitions between detrapped and trapped states and the only fitting parameters are those of the traps (energy level and concentration) and the Huang-Rhys factor. Therefore, dependences of the trapping and detrapping processes on the bias, position, and temperature can be obtained with this model. The results of the model are compared with experimental data of stress induced leakage current in metal-oxide-semiconductor devices. The average energy loss has been obtained and an interpretation is given of the curves of average energy loss versus oxide voltage. This allows us to identify the entrance of the assisted tunnel current in the Fowler-Nordheim regime. In addition, the dependence of the tunnel current and average energy loss on the model parameters has been studied.

  7. A thermo dynamical model for the shape and size effect on melting of boron carbide nanoparticles.

    Science.gov (United States)

    Antoniammal, Paneerselvam; Arivuoli, Dakshanamoorthy

    2012-02-01

    The size and shape dependence of the melting temperature of Boron Carbide (B4C) nanoparticles has been investigated with a numerical thermo dynamical approach. The problem considered in this paper is the inward melting of nanoparticles with spherical and cylindrical geometry. The cylindrical Boron Carbide (B4C) nanoparticles, whose melting point has been reported to decrease with decreasing particle radius, become larger than spherical shaped nanoparticle. Comparative investigation of the size dependence of the melting temperature with respect to the two shapes is also been done. The melting temperature obtained in the present study is approximately a dealing function of radius, in a good agreement with prediction of thermo dynamical model.

  8. Thermal conductivity modeling of water containing metal oxide nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Ahmad Azari

    2015-01-01

    The nano particles have demonstrated great potential to improve the heat transfer characteristics of heat transfer fluids. Possible parameters responsible for this increase were studied. The heat transfer profile in the nanolayer region was combined with other parameters such as volume fraction, particle radius thermal conductivity of the fluid, particle and nanolayer, to formulate a thermal conductivity model. Results predicting the thermal conductivity of nanofluids using the model were compared with experimental results as well as studies by other researchers. The comparison of the results obtained for the CuO/water and TiO2/water nanofluids studied shows that the correlation proposed is in closest proximity in predicting the experimental results for the thermal conductivity of a nanofluid. Also, a parametric study was performed to understand how a number of factors affect the thermal conductivity of nanofluids using the developed correlation.

  9. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander;

    2015-01-01

    Hydrogen oxidation at 50 bar and temperatures of 700–900 K was investigated in a high pressure laminar flow reactor under highly diluted conditions. The experiments provided information about H 2 oxidation at pressures above the third explosion limit. The fuel–air equivalence ratio of the reactants...... for the reactions HO 2 + OH, OH + OH, and HO 2 +HO 2 were updated based on recent determinations. The modeling pre- dictions were in good agreement with the measurements in the flow reactor. The predicted H 2 oxidation rate was sensitive to the rate of the HO 2 + OH reaction, particularly at lean conditions......, and the present data sup- port recent values for the rate constant. In addition to the current experiments, the mechanism was evaluated against ignition delay time measurements from rapid compression machines and shock tubes. The model was used to analyze the complex dependence of the ignition delay for H 2...

  10. Physiologically based pharmacokinetic models for trichloroethylene and its oxidative metabolites.

    OpenAIRE

    Fisher, J W

    2000-01-01

    Trichloroethylene (TCE) pharmacokinetics have been studied in experimental animals and humans for over 30 years. Compartmental and physiologically based pharmacokinetic (PBPK) models have been developed for the uptake, distribution, and metabolism of TCE and the production, distribution, metabolism, and elimination of P450-mediated metabolites of TCE. TCE is readily taken up into systemic circulation by oral and inhalation routes of exposure and is rapidly metabolized by the hepatic P450 syst...

  11. 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

  12. Recent Advances in Modeling Transition Metal Oxides for Photo-electrochemistry

    Science.gov (United States)

    Caspary Toroker, Maytal

    Computational research offers a wide range of opportunities for materials science and engineering, especially in the energy arena where there is a need for understanding how material composition and structure control energy conversion, and for designing materials that could improve conversion efficiency. Potential inexpensive materials for energy conversion devices are metal oxides. However, their conversion efficiency is limited by at least one of several factors: a too large band gap for efficiently absorbing solar energy, similar conduction and valence band edge characters that may lead to unfavorably high electron-hole recombination rates, a valence band edge that is not positioned well for oxidizing water, low stability, low electronic conductivity, and low surface reactivity. I will show how we model metal oxides with ab-initio methods, primarily DFT +U. Our previous results show that doping with lithium, sodium, or hydrogen could improve iron (II) oxide's electronic properties, and alloying with zinc or nickel could improve iron (II) oxide's optical properties. Furthermore, doping nickel (II) oxide with lithium could improve several key properties including solar energy absorption. In this talk I will highlight new results on our understanding of the mechanism of iron (III) oxide's surface reactivity. Our theoretical insights bring us a step closer towards understanding how to design better materials for photo-electrochemistry. References: 1. O. Neufeld and M. Caspary Toroker, ``Pt-doped Fe2O3 for enhanced water splitting efficiency: a DFT +U study'', J. Phys. Chem. C 119, 5836 (2015). 2. M. Caspary Toroker, ``Theoretical Insights into the Mechanism of Water Oxidation on Non-stoichiometric and Ti - doped Fe2O3 (0001)'', J. Phys. Chem. C, 118, 23162 (2014). This research was supported by the Morantz Energy Research Fund, the Nancy and Stephen Grand Technion Energy Program, the I-CORE Program of the Planning and Budgeting Committee, and The Israel Science

  13. A Coarse-Grained Model for Polyethylene Oxide and Polyethylene Glycol : Conformation and Hydrodynamics

    NARCIS (Netherlands)

    Lee, Hwankyu; de Vries, Alex H.; Marrink, Siewert-Jan; Pastor, Richard W.

    2009-01-01

    A coarse-grained (CG) model for polyethylene oxide (PEO) and polyethylene glycol (PEG) developed within the framework of the MARTINI CG force field (FF) using the distributions of bonds, angles, and dihedrals from the CHARMM all-atom FF is presented. Densities of neat low molecular weight PEO agree

  14. Therapeutic attenuation of mitochondrial dysfunction and oxidative stress in neurotoxin models of Parkinson's disease

    OpenAIRE

    Stack, Edward C.; Ferro, Joellyn L.; Kim, Jinho; Del Signore, Steven J.; Goodrich, Sarah; Matson, Samantha; Hunt, Bonnie B.; Cormier, Kerry; Smith, Karen; Matson, Wayne R.; Ryu, Hoon; Ferrante, Robert J.

    2008-01-01

    Therapeutic attenuation of mitochondrial dysfunction and oxidative stress in neurotoxin models of Parkinson?s disease correspondence: Corresponding author. GRECC Unit 182B, Bedford VA Medical Center, 200 Springs Road, Bedford, MA 01730, USA. Tel.: +1 781 687 2908; fax: +1 781 687 3515. (Ferrante, Robert J.) (Ferrante, Robert J.) Department of Neurology, Boston University School of Medicine - Boston--> , MA 02118--> ...

  15. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten;

    2010-01-01

    Density functional theory calculations have been performed for the three elementary steps―Tafel, Heyrovsky, and Volmer―involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively char...

  16. A detailed approach to model transport, heterogeneous chemistry, and electrochemistry in solid-oxide fuel cells

    OpenAIRE

    Janardhanan, Vinod

    2007-01-01

    This book lays out a numerical framework for the detailed description of heterogeneous chemistry, electrochemistry and porous media transport in solid-oxide fuel cells (SOFC). Assuming hydrogen as the only electrochemically active species, a modified Butler-Volmer equation is used to model the electrochemical charge transfer.

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

    Energy Technology Data Exchange (ETDEWEB)

    Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F. [Vanderbilt Univ., Nashville, TN (United States); Michez, A. [Univ. Montpellier 2 (France); Fleetwood, D.M. [Sandia National Labs., Albuquerque, NM (United States); Witczak, S.C. [Aerospace Corp., Los Angeles, CA (United States)

    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.

  18. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    Science.gov (United States)

    Abraham, Martin; Fisher, John W.

    1995-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  19. Kinetic modeling of the oxidative degradation of additive free PE in bleach disinfected water

    Science.gov (United States)

    Mikdam, Aïcha; Colin, Xavier; Billon, Noëlle; Minard, Gaëlle

    2016-05-01

    The chemical interactions between PE and bleach were studied at 60°C in immersion in bleach solutions kept at a free chlorine concentration of 100 ppm and a pH of 5 or 7.2. It was found that the polymer undergoes a severe oxidation from the earliest weeks of exposure, in a superficial layer whose thickness (of about 50-70 µm) is almost independent of the pH value, although the superficial oxidation rate is faster in acidic than in neutral medium. Oxidation leads to the formation and accumulation of a large variety of carbonyl products (mostly ketones and carboxylic acids) and, after a few weeks, to a decrease in the average molar mass due to the large predominance of chain scissions over crosslinking. A scenario was elaborated for explaining such unexpected results. According to this scenario, the non-ionic molecules (Cl2 and ClOH) formed from the disinfectant in the water phase, would migrate deeply into PE and dissociate into highly reactive radicals (Cl• and HO•) in order to initiate a radical chain oxidation. A kinetic model was derived from this scenario for predicting the general trends of the oxidation kinetics and its dependence on environmental factors such as temperature, free chlorine concentration and pH. The validity of this model was successfully checked by comparing the numerical simulations with experimental data.

  20. Development of Linear Irreversible Thermodynamic Model for Oxidation Reduction Potential in Environmental Microbial System

    Science.gov (United States)

    Cheng, Hong-Bang; Kumar, Mathava; Lin, Jih-Gaw

    2007-01-01

    Nernst equation has been directly used to formulate the oxidation reduction potential (ORP) of reversible thermodynamic conditions but applied to irreversible conditions after several assumptions and/or modifications. However, the assumptions are sometimes inappropriate in the quantification of ORP in nonequilibrium system. We propose a linear nonequilibrium thermodynamic model, called microbial related reduction and oxidation reaction (MIRROR Model No. 1) for the interpretation of ORP in biological process. The ORP was related to the affinities of catabolism and anabolism. The energy expenditure of catabolism and anabolism was directly proportional to overpotential (η), straight coefficient of electrode (LEE), and degree of coupling between catabolism and ORP electrode, respectively. Finally, the limitations of MIRROR Model No. 1 were discussed for expanding the applicability of the model. PMID:17496027

  1. Modelling nitrous oxide emission from soils. A tool for exploring emission reduction strategies

    Energy Technology Data Exchange (ETDEWEB)

    Langeveld, C.A.; Leffelaar, P.A.; Goudriaan, J. [Dept. of Theoretical Production Ecology, Wageningen Agricultural Univ. (Netherlands)

    1995-11-01

    Possibilities to reduce nitrous oxide (N{sub 2}O) emission from soils can be explored with simulation models. In this study, principal assumptions and hypotheses underlying such a simulation model under development are presented. It uses soil water content profiles as main input data and describes production, consumption and transport of N{sub 2}O. Observations on sandy grassland plots in the Wageningen Rhizolab will be used in the model development. The model is to explain the shape of the nitrous oxide profiles and the relation between subsurface nitrous oxide gradients and the observed fluxes. Soils are estimated to be responsible for more than 50 % of the global emission of N{sub 2}O. Soil emission data show a large variation. This variation results from the influence of various factors on the fundamental processes denitrification, nitrification and transport that determine N{sub 2}O emission from soils. These factors are temperature, aeration (related to moisture content), nitrogen mineralisation rate, amount and kind of added N fertilizer and content of readily decomposable carbohydrates. The current research is focussed on quantifying and modelling the influence of these factors on N{sub 2}O emission from grassland soils. Some of the above-mentioned factors, like aeration and fertilization, can be manipulated in soils. These possibilities can be explored in experiments. Simulation models can be a powerful tool to guide this experimental work and to minimise the amount of work needed for giving well-based proposals for strategies to reduce N{sub 2}O emissions from soils. In this paper the planned development, calibration and validation of a simulation model to describe nitrous oxide dynamics in and emission from relatively homogeneous grassland soils are outlined. In these modelling steps results of experiments in the Wageningen Rhizolab will be used. 1 fig., 12 refs.

  2. 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

  3. Experimental and Modeling Investigation of the Low-Temperature Oxidation of Dimethyl Ether.

    Science.gov (United States)

    Rodriguez, Anne; Frottier, Ophélie; Herbinet, Olivier; Fournet, René; Bounaceur, Roda; Fittschen, Christa; Battin-Leclerc, Frédérique

    2015-07-16

    The oxidation of dimethyl ether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K; equivalence ratios of 0.25, 1, and 2; residence time of 2 s; pressure of 106.7 kPa (close to the atmospheric pressure); and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring-down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde, which is one of the major products from DME oxidation, as well as that of hydrogen peroxide, which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bars on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine, and flame data from literature. The kinetic analysis of the model enabled the highlighting of some specificities of the oxidation chemistry of DME: (1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H atom abstraction) with oxygen yielding an olefin + HO2·; (2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting

  4. Experimental and Modeling Investigation of the Low-Temperature Oxidation of Dimethyl Ether.

    Science.gov (United States)

    Rodriguez, Anne; Frottier, Ophélie; Herbinet, Olivier; Fournet, René; Bounaceur, Roda; Fittschen, Christa; Battin-Leclerc, Frédérique

    2015-07-16

    The oxidation of dimethyl ether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K; equivalence ratios of 0.25, 1, and 2; residence time of 2 s; pressure of 106.7 kPa (close to the atmospheric pressure); and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring-down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde, which is one of the major products from DME oxidation, as well as that of hydrogen peroxide, which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bars on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine, and flame data from literature. The kinetic analysis of the model enabled the highlighting of some specificities of the oxidation chemistry of DME: (1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H atom abstraction) with oxygen yielding an olefin + HO2·; (2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting

  5. 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 oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. PMID:26551878

  6. Thermodynamic Model and Database for Sulfides Dissolved in Molten Oxide Slags

    Science.gov (United States)

    Kang, Youn-Bae; Pelton, Arthur D.

    2009-12-01

    A thermodynamic model has been developed in the framework of the modified quasichemical model in the quadruplet approximation to permit the calculation of solubilities of various gaseous species (sulfide, sulfate, nitride, carbide, water, etc.) in molten slags. The model calculates the solubilities solely from knowledge of the thermodynamic activities of the component oxides and the Gibbs energies of the pure liquid components (oxides, sulfides, sulfates, etc.). In the current article, it is shown that solubilities of sulfur as sulfide in Al2O3-CaO-FeO-Fe2O3-MgO-MnO-SiO2-TiO2-Ti2O3 multicomponent slags, which are predicted from the current model with no adjustable model parameters, are in good agreement with all available experimental data. The article also provides a thorough review of experimental sulfide capacity data for this system. The model applies at all compositions from pure oxides to pure sulfides and from basic to acidic slags. By coupling this database with other evaluated databases, such as those for molten metal and gaseous phases, and with general software for Gibbs energy minimization, practically important slag/metal/gas/solid equilibria can be computed such as S-distribution ratios.

  7. A model bismuth oxide intergranular thin film in a ZnO twist grain boundary

    Energy Technology Data Exchange (ETDEWEB)

    Domingos, H S [INESC, Microsistemas and Nanotecnologias, Rua Alves Redol 1-9, P-1000-029 Lisbon (Portugal)

    2010-04-14

    The electronic properties of a model bismuth oxide intergranular film in ZnO were investigated using density functional plane wave calculations. It was found that oxygen excess plays a fundamental role in the appearance of electrical activity. The introduction by oxygen interstitials or zinc vacancies results in depletion of the charge in deep gap states introduced by the bismuth impurities. This makes the boundary less metallic and promotes the formation of acceptor states localized to the boundary core, resulting in Schottky barrier enhancement. The results indicate that the origin of electrical activity in thin intergranular bismuth oxide films is probably not distinct from that in decorated ZnO boundaries.

  8. Modeling Low-Dose-Rate Effects in Irradiated Bipolar-Base Oxides

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-10-26

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in bipolar junction transistors. Multiple-trapping simulations show that space charge limited transport is partially responsible for low-dose-rate enhancement. At low dose rates, more holes are trapped near the silicon-oxide interface than at high dose rates, resulting in larger midgap voltage shifts at lower dose rates. The additional trapped charge near the interface may cause an exponential increase in excess base current, and a resultant decrease in current gain for some NPN bipolar technologies.

  9. In-pile steam oxidation of model HTGR fuel elements

    International Nuclear Information System (INIS)

    Model HTGR fuel elements were exposed to various concentrations of steam while being irradiated under several sets of temperature conditions in the Oak Ridge Research Reactor. In one test, catalysis by iron impurities in the graphite casing of the fuel element caused a highly localized attack on the graphite by the steam; this resulted in the formation of deep pits in the casing. Furthermore, the iron impurities were sufficiently mobile to cause pitting attack on the pyrolytic carbon coatings of the fuel particles as well. The presence of steam induced a rapid increase in the release of gaseous fission products. However, the cessation of steam ingress in the primary system resulted in a pronounced, but correspondingly smaller, reduction in the level of gaseous release. The incidence of fuel failure was greater than anticipated; however, even though the coatings of greater than 30% of the fuel had failed, the release of fission products beyond the fuel element itself was largely confined to iodine and the noble gases. A novel mode of fuel failure was observed under the rather severe conditions of the tests; this involved the attack of the pyrolytic carbon coatings on intact particles by uncoated fragments of uranium fuel kernel material from failed particles

  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. 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

  12. Modeling of tunneling current in ultrathin MOS structure with interface trap charge and fixed oxide charge

    Institute of Scientific and Technical Information of China (English)

    Hu Bo; Huang Shi-Hua; Wu Feng-Min

    2013-01-01

    A model based on analysis of the self-consistent Poisson-Schrodinger equation is proposed to investigate the tunneling current of electrons in the inversion layer of a p-type metal-oxide-semiconductor (MOS) structure.In this model,the influences of interface trap charge (ITC) at the Si-SiO2 interface and fixed oxide charge (FOC) in the oxide region are taken into account,and one-band effective mass approximation is used.The tunneling probability is obtained by employing the transfer matrix method.Further,the effects of in-plane momentum on the quantization in the electron motion perpendicular to the Si-SiO2 interface of a MOS device are investigated.Theoretical simulation results indicate that both ITC and FOC have great influence on the tunneling current through a MOS structure when their densities are larger than 1012 cm-2,which results from the great change of bound electrons near the Si-SiO2 interface and the oxide region.Therefore,for real ultrathin MOS structures with ITC and FOC,this model can give a more accurate description for the tunneling current in the inversion layer.

  13. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    Science.gov (United States)

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  14. microRNAs: Emerging Targets Regulating Oxidative Stress in the Models of Parkinson's Disease.

    Science.gov (United States)

    Xie, Yangmei; Chen, Yinghui

    2016-01-01

    Parkinson's disease (PD) is the second most common neurodegenerative disorder. This chronic, progressive disease is characterized by loss of dopaminergic (DA) neurons in the substantia nigra pars compacta (SNpc) and the presence of cytoplasmic inclusions called Lewy bodies (LBs) in surviving neurons. PD is attributed to a combination of environment and genetic factors, but the precise underlying molecular mechanisms remain elusive. Oxidative stress is generally recognized as one of the main causes of PD, and excessive reactive oxygen species (ROS) can lead to DA neuron vulnerability and eventual death. Several studies have demonstrated that small non-coding RNAs termed microRNAs (miRNAs) can regulate oxidative stress in vitro and in vivo models of PD. Relevant miRNAs involved in oxidative stress can prevent ROS-mediated damage to DA neurons, suggesting that specific miRNAs may be putative targets for novel therapeutic targets in PD. PMID:27445669

  15. 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.

  16. Nitronate monooxygenase, a model for anionic flavin semiquinone intermediates in oxidative catalysis.

    Science.gov (United States)

    Gadda, Giovanni; Francis, Kevin

    2010-01-01

    Nitronate monooxygenase (NMO), formerly referred to as 2-nitropropane dioxygenase, is an FMN-dependent enzyme that uses molecular oxygen to oxidize (anionic) alkyl nitronates and, in the case of the enzyme from Neurospora crassa, (neutral) nitroalkanes to the corresponding carbonyl compounds and nitrite. Over the past 5 years, a resurgence of interest on the enzymology of NMO has driven several studies aimed at the elucidation of the mechanistic and structural properties of the enzyme. This review article summarizes the knowledge gained from these studies on NMO, which has been emerging as a model system for the investigation of anionic flavosemiquinone intermediates in the oxidative catalysis of organic molecules, and for the effect that branching of reaction intermediates has on both the kinetic parameters and isotope effects associated with enzymatic reactions. A comparison of the catalytic mechanism of NMO with other flavin-dependent enzymes that oxidize nitroalkane and nitronates is also presented. PMID:19577534

  17. Alternative Fabrication Routes toward Oxide-Dispersion-Strengthened Steels and Model Alloys

    Science.gov (United States)

    Bergner, Frank; Hilger, Isabell; Virta, Jouko; Lagerbom, Juha; Gerbeth, Gunter; Connolly, Sarah; Hong, Zuliang; Grant, Patrick S.; Weissgärber, Thomas

    2016-07-01

    The standard powder metallurgy (PM) route for the fabrication of oxide-dispersion-strengthened (ODS) steels involves gas atomization to produce a prealloyed powder, mechanical alloying (MA) with fine oxide powders, consolidation, and finally thermal/thermomechanical treatment (TMT). It is well established that ODS steels with superior property combinations, for example, creep and tensile strength, can be produced by this PM/MA route. However, the fabrication process is complex and expensive, and the fitness for scaling up to the industrial scale is limited. At the laboratory scale, production of small amounts of well-controlled model systems continues to be desirable for specific purposes, such as modeling-oriented experiments. Thus, from the laboratory to industrial application, there is growing interest in complementary or alternative fabrication routes for ODS steels and related model systems, which offer a different balance of cost, convenience, properties, and scalability. This article reviews the state of the art in ODS alloy fabrication and identifies promising new routes toward ODS steels. The PM/AM route for the fabrication of ODS steels is also described, as it is the current default process. Hybrid routes that comprise aspects of both the PM route and more radical liquid metal (LM) routes are suggested to be promising approaches for larger volumes and higher throughput of fabricated material. Although similar uniformity and refinement of the critical nanometer-sized oxide particles has not yet been demonstrated, ongoing innovations in the LM route are described, along with recent encouraging preliminary results for both extrinsic nano-oxide additions and intrinsic nano-oxide formation in variants of the LM route. Finally, physicochemical methods such as ion beam synthesis are shown to offer interesting perspectives for the fabrication of model systems. As well as literature sources, examples of progress in the authors' groups are also highlighted.

  18. Alternative Fabrication Routes toward Oxide-Dispersion-Strengthened Steels and Model Alloys

    Science.gov (United States)

    Bergner, Frank; Hilger, Isabell; Virta, Jouko; Lagerbom, Juha; Gerbeth, Gunter; Connolly, Sarah; Hong, Zuliang; Grant, Patrick S.; Weissgärber, Thomas

    2016-11-01

    The standard powder metallurgy (PM) route for the fabrication of oxide-dispersion-strengthened (ODS) steels involves gas atomization to produce a prealloyed powder, mechanical alloying (MA) with fine oxide powders, consolidation, and finally thermal/thermomechanical treatment (TMT). It is well established that ODS steels with superior property combinations, for example, creep and tensile strength, can be produced by this PM/MA route. However, the fabrication process is complex and expensive, and the fitness for scaling up to the industrial scale is limited. At the laboratory scale, production of small amounts of well-controlled model systems continues to be desirable for specific purposes, such as modeling-oriented experiments. Thus, from the laboratory to industrial application, there is growing interest in complementary or alternative fabrication routes for ODS steels and related model systems, which offer a different balance of cost, convenience, properties, and scalability. This article reviews the state of the art in ODS alloy fabrication and identifies promising new routes toward ODS steels. The PM/AM route for the fabrication of ODS steels is also described, as it is the current default process. Hybrid routes that comprise aspects of both the PM route and more radical liquid metal (LM) routes are suggested to be promising approaches for larger volumes and higher throughput of fabricated material. Although similar uniformity and refinement of the critical nanometer-sized oxide particles has not yet been demonstrated, ongoing innovations in the LM route are described, along with recent encouraging preliminary results for both extrinsic nano-oxide additions and intrinsic nano-oxide formation in variants of the LM route. Finally, physicochemical methods such as ion beam synthesis are shown to offer interesting perspectives for the fabrication of model systems. As well as literature sources, examples of progress in the authors' groups are also highlighted.

  19. Modeling the oxidative coupling of methane:Heterogeneous chemistry coupled with 3D flow field simulation

    Institute of Scientific and Technical Information of China (English)

    Yaghobi Nakisa; Ghoreishy Mir Hamid Reza

    2009-01-01

    The oxidative coupling of methane (OCM) over titanate perovskite catalyst has been developed by three-dimensional numerical simulations of flow field coupled with heat transfer as well as heterogeneous kinetic model.The reaction was assumed to take place both in the gas phase and on the catalytic surface.Kinetic rate constants were experimentally obtained using a ten step kinetic model.The simulation results agree quite well with the data of OCM experiments,which were used to investigate the effect of temperature on the selectivity and conversion obtained in the methane oxidative coupling process.The conversion of methane linearly increased with temperature and the selectivity of C2 was practically constant in the temperature range of 973-1073 K.The study shows that CFD tools make it possible to implement the heterogeneous kinetic model even for high exothermic reaction such as OCM.

  20. Detection and quantification of protein oxidation in sarcopenic models: a mass spectrometry study.

    Science.gov (United States)

    Pasha, Sabah; Tveen Jensen, Karina; Pitt, Andrew R; Spickett, Corinne M

    2014-10-01

    Oxidised biomolecules in aged tissue could potentially be used as biomarkers for age-related diseases; however, it is still unclear whether they causatively contribute to ageing or are consequences of the ageing process. To assess the potential of using protein oxidation as markers of ageing, mass spectrometry (MS) was employed for the identification and quantification of oxidative modifications in obese (ob/ob) mice. Lean muscle mass and strength is reduced in obesity, representing a sarcopenic model in which the levels of oxidation can be evaluated for different muscular systems including calcium homeostasis, metabolism and contractility. Several oxidised residues were identified by tandem MS (MS/MS) in both muscle homogenate and isolated sarcoplasmic reticulum (SR), an organelle that regulates intracellular calcium levels in muscle. These modifications include oxidation of methionine, cysteine, tyrosine, and tryptophan in several proteins such as sarcoplasmic reticulum calcium ATPase (SERCA), glycogen phosphorylase, and myosin. Once modifications had been identified, multiple reaction monitoring MS (MRM) was used to quantify the percentage modification of oxidised residues within the samples. Preliminary data suggests proteins in ob/ob mice are more oxidised than the controls. For example SERCA, which constitutes 60-70% of the SR, had approximately a 2-fold increase in cysteine trioxidation of Cys561 in the obese model when compared to the control. Other obese muscle proteins have also shown a similar increase in oxidation for various residues. Further analysis with complex protein mixtures will determine the potential diagnostic use of MRM experiments for analysing protein oxidation in small biological samples such as muscle needle biopsies. PMID:26461380

  1. Titanium oxide modeling and design for innovative biomedical surfaces: a concise review.

    Science.gov (United States)

    De Nardo, Luigi; Raffaini, Giuseppina; Ebramzadeh, Edward; Ganazzoli, Fabio

    2012-09-01

    The natural oxide layer on implantable alloys insulates the reactive underlying metal from the physiological environment, preventing substrate corrosion and device failure. This type of oxide film has had a major role in the minimization of functional failure and toxic response after implantation in the first generation biomaterials. Recent advances in theoretical, computational, and experimental surface engineering tools provide the foundation for the design of novel devices with improved performances in this regard based on conventional implantable metal alloys. An increasing number of technologies provide the possibility of tailoring chemico-physical and morphological parameters of the surface oxide layers. For some applications, such as dental implants, surface modifications result in substantial innovation and economic success. However, the selection of novel surfaces is in general based on experimental studies and has a limited theoretical and computational foundation. In this review, we offer a perspective analysis of the correlation between theoretical studies and chemical surface modification technologies, with a special emphasis on titanium oxide on Ti alloys. Theoretical approaches for the surface behavior at an atomistic level of description are presented, together with some adsorption studies on a rutile surface. The role of chemical and electrochemical surface modification technologies in modifying the TiO(2) structure, morphology, and chemistry to tailor in vivo biological response is then briefly reviewed. Finally, we discuss the role of surface modeling as a powerful design tool for a new generation of implantable devices in which metal oxide surface can be tuned to yield specific biological response.

  2. Pharmacological models and approaches for pathophysiological conditions associated with hypoxia and oxidative stress.

    Science.gov (United States)

    Farías, Jorge G; Herrera, Emilio A; Carrasco-Pozo, Catalina; Sotomayor-Zárate, Ramón; Cruz, Gonzalo; Morales, Paola; Castillo, Rodrigo L

    2016-02-01

    Hypoxia is the failure of oxygenation at the tissue level, where the reduced oxygen delivered is not enough to satisfy tissue demands. Metabolic depression is the physiological adaptation associated with reduced oxygen consumption, which evidently does not cause any harm to organs that are exposed to acute and short hypoxic insults. Oxidative stress (OS) refers to the imbalance between the generation of reactive oxygen species (ROS) and the ability of endogenous antioxidant systems to scavenge ROS, where ROS overwhelms the antioxidant capacity. Oxidative stress plays a crucial role in the pathogenesis of diseases related to hypoxia during intrauterine development and postnatal life. Thus, excessive ROS are implicated in the irreversible damage to cell membranes, DNA, and other cellular structures by oxidizing lipids, proteins, and nucleic acids. Here, we describe several pathophysiological conditions and in vivo and ex vivo models developed for the study of hypoxic and oxidative stress injury. We reviewed existing literature on the responses to hypoxia and oxidative stress of the cardiovascular, renal, reproductive, and central nervous systems, and discussed paradigms of chronic and intermittent hypobaric hypoxia. This systematic review is a critical analysis of the advantages in the application of some experimental strategies and their contributions leading to novel pharmacological therapies. PMID:26617218

  3. 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

    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...... the four denitrification steps, the last one (N2O reduction to N2) seems to be inhibited first when O2 is present. Overall, N2O 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...

  4. Effect of Intramuscular Injection on Oxidative Homeostasis in Laboratory Guinea Pig Model.

    Science.gov (United States)

    Kračmarová, Alžběta; Banďouchová, Hana; Pikula, Jiří; Pohanka, Miroslav

    2016-01-01

    In animal models, there was observed alteration of various physiological processes caused by microtraumas. Here reported experiment was aimed on the research of link between injection and development of an oxidative imbalance. Laboratory guinea pig was chosen as a suitable model for examining of the oxidative stress. Markers indicating oxidative homeostasis were assayed in the frontal, temporal and occipital brain lobe, cerebellum, liver, kidney, spleen and heart one hour after an intramuscular injection. Common biochemical parameters were measured in plasma samples as well. The most extensive effect was observed in the heart where the thiobarbituric acid reactive substances value was more than twice increased after the injection. The level of carbonylated proteins was significantly elevated in the kidney and ferric reducing antioxidant power value was increased in the brain compartments. The enzyme activities in the organs were not influenced except the activity of superoxide dismutase, which was moderately decreased in the brain. In the plasma samples, there was observed increase of the blood urea nitrogen. The results showed significant the influence of the intramuscular injection on a development of an oxidative insult. The injection can be considered as an adverse effect with quite extensive stress consequences. PMID:27526307

  5. ZORO 1: a finite difference computer model for Zircaloy-4 oxidation in steam

    Energy Technology Data Exchange (ETDEWEB)

    Dobson, W.G.; Biederman, R.R.

    1976-12-01

    A user's manual is presented for the ZORO 1 computer code developed in conjunction with the EPRI research program RP 249-1. ZORO 1 characterizes the oxidation behavior of Zircaloy-4 in steam using a finite difference analytical technique for oxygen diffusion into the cladding. While specifically developed to characterize oxidation of Zircaloy-4 in steam, the modeling used in ZORO 1 is general and capable of handling any two- or three-phase system with one element diffusing under transient temperature-time conditions. In this model, the fundamental variables of oxygen diffusion and interface oxygen concentrations associated with phase equilibrium are required along with the desired temperature transient. Output includes oxide and xi thicknesses, an oxygen concentration gradient in all phases present, oxygen absorbed in each phase, total oxygen absorbed and a prediction of ..cap alpha.. incursion formation based on oxygen saturation of the ..beta.. phase. Several options are included for convenience of the user. The purpose of this report is to present the ZORO 1 computer code in a convenient form for use. Examples of prediction capability for a variety of oxidation events are demonstrated to explain various input and output options available in the ZORO 1 computer code.

  6. Process flow model of solid oxide fuel cell system supplied with sewage biogas

    OpenAIRE

    Van herle, Jan; Favrat, Daniel; Maréchal, François; Bucheli, Olivier; Leuenberger, Sacha; Membrez, Yves

    2004-01-01

    A model for a 1000 kW class solid oxide fuel cell (SOFC) system running on biogas from a sewage sludge digestion plant was implemented in a process flow scheme using external steam reforming. The model stack consisted of planar anode supported cells operated at 800 degreesC displaying state-of- the-art electrochemical performance (0.15 W/cm(2) at 80% fuel utilisation). Real annual data from an existing sewage plant were used as input to the model. From the input of 43 m(3)/h biogas (63% ...

  7. Model-fitting approach to kinetic analysis of non-isothermal oxidation of molybdenite

    International Nuclear Information System (INIS)

    The kinetics of molybdenite oxidation was studied by non-isothermal TGA-DTA with heating rate 5degC.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 108 sec-1 for extent of reaction less than 0.5

  8. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    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

  9. 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

  10. Ionic conductivity studies of solid oxide fuel cell electrolytes and theoretical modeling of an entire solid oxide fuel cell

    Science.gov (United States)

    Pornprasertsuk, Rojana

    Because of the steep increase in oil prices, the global warming effect and the drive for energy independence, alternative energy research has been encouraged worldwide. The sustainable fuels such as hydrogen, biofuel, natural gas, and solar energy have attracted the attention of researchers. To convert these fuels into a useful energy source, an energy conversion device is required. Fuel cells are one of the energy conversion devices which convert chemical potentials into electricity. Due to their high efficiency, the ease to scale from 1 W range to megawatts range, no recharging requirement and the lack of CO2 and NOx emission (if H2 and air/O 2 are used), fuel cells have become a potential candidate for both stationary power generators and portable applications. This thesis has been focused primarily on solid oxide fuel cell (SOFC) studies due to its high efficiency, varieties of fuel choices, and no water management problem. At the present, however, practical applications of SOFCs are limited by high operating temperatures that are needed to create the necessary oxide-ion vacancy mobility in the electrolyte and to create sufficient electrode reactivities. This thesis introduces several experimental and theoretical approaches to lower losses both in the electrolyte and the electrodes. Yttria stabilized zirconia (YSZ) is commonly used as a solid electrolyte for SOFCs due to its high oxygen-ion conductivity. To improve the ionic conductivity for low temperature applications, an approach that involves dilating the structure by irradiation and introducing edge dislocations into the electrolyte was studied. Secondly, to understand the activation loss in SOFC, the kinetic Monte Carlo (KMC) technique was implemented to model the SOFC operation to determining the rate-limiting step due to the electrodes on different sizes of Pt catalysts. The isotope exchange depth profiling technique was employed to investigate the irradiation effect on the ionic transport in different

  11. Modeling selenite adsorption envelopes on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenite adsorption behavior was investigated on amorphous aluminum and iron oxides, clay minerals: kaolinite, montmorillonite, and illite, and 45 surface and subsurface soil samples from the Southwestern and Midwestern regions of the USA as a function of solution pH. Selenite adsorption decreased ...

  12. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    Science.gov (United States)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  13. Mesoscale modeling of combined aerosol and photo-oxidant processes in the Eastern Mediterranean

    Science.gov (United States)

    Lazaridis, M.; Spyridaki, A.; Solberg, S.; Smolík, J.; Zdímal, V.; Eleftheriadis, K.; Aleksanropoulou, V.; Hov, O.; Georgopoulos, P. G.

    2005-03-01

    Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13-16 July 2000, 26-30 July 2000 and 7-14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. The objective of the current modeling work was mainly to apply the UAM-AERO mesoscale model in the eastern Mediterranean in order to assess the performed field campaigns and determine that the applied mesoscale model is fit for this purpose. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer and winter campaigns. Discrepancies between modeled and measured data are attributed to unresolved particulate matter emissions. Particulate matter in the area is mainly composed by sulphate, sea salt and crustal materials, and with significant amounts of nitrate, ammonium and organics. During winter the particulate matter and oxidant concentrations were lower than the summer values.

  14. Comparisons between box and global model simulations of chemical oxidation in the tropical marine boundary layer

    Science.gov (United States)

    Heard, Dwayne; Stone, Daniel; Vaughan, Stewart; Ingham, Trevor; Whalley, Lisa; Evans, Mat; Read, Katie; Lee, James; Moller, Sarah; Carpenter, Lucy; Lewis, Alastair

    2013-04-01

    Atmospheric oxidation processes during the daytime are dominated by the OH radical, particularly in the tropical marine boundary layer, where the warm, humid conditions and high solar irradiation lead to high OH production rates. Atmospheric models have shown that such high OH production rates in tropical regions lead to a significant fraction of global methane oxidation in tropical regions. Understanding the processes controlling OH concentrations, and thus the extent of methane oxidation, in tropical regions is therefore essential to our understanding of the global oxidising capacity and for accurate climate change predictions. Long-term measurements of OH, and the closely coupled HO2 radical, were made using the FAGE (Fluorescence Assay by Gas Expansion) technique at the Cape Verde Atmospheric Observatory (16.85 N, 24.87 W) on the island of Sao Vicente as part of the Seasonal Oxidant Study (SOS) in the tropical Atlantic during three distinct seasonal periods in February-March, June and September 2009 (Vaughan et al., ACP, 12, 2149, 2012). In this paper we describe model simulations of OH and HO2 radicals with both a heavily constrained box model using the Dynamically Simple Model of Atmospheric Chemical Complexity (DSMACC), based on the Master Chemical Mechanism (MCM v3.2, extended with a halogen chemistry scheme), and the three-dimensional global chemistry transport model GEOS-Chem (v9-01-03, including recent updates to include bromine chemistry). The box model calculations indicate that solar photolysis of ozone is responsible for over 80 % of midday radical production, with photolysis of HCHO contributing a further 9 % of the total midday radical production. Radical losses at midday are dominated by CH3O2 + HO2 (26 %), uptake of HO2 onto aerosol surfaces (21 %) and HO2+ HO2 (18 %). Both model approaches result in an overprediction of OH and HO2, potentially arising from incomplete consideration of radical sinks. However, the two model approaches differ in the

  15. Effects of nitric oxide-related compounds in the acute ketamine animal model of schizophrenia

    OpenAIRE

    Kandratavicius, Ludmyla; Balista, Priscila Alves; Wolf, Daniele Cristina; Abrao, Joao; Evora, Paulo Roberto; Rodrigues, Alfredo Jose; Chaves, Cristiano; Maia-de-Oliveira, Joao Paulo; Leite, Joao Pereira; Dursun, Serdar Murat; Baker, Glen Bryan; Guimaraes, Francisco Silveira; Hallak, Jaime Eduardo Cecilio

    2015-01-01

    Background Better treatments for schizophrenia are urgently needed. The therapeutic use of the nitric oxide (NO)-donor sodium nitroprusside (SNP) in patients with schizophrenia has shown promising results. The role of NO in schizophrenia is still unclear, and NO modulation is unexplored in ketamine (KET) animal models to date. In the present study, we compared the behavioral effects of pre- and post-treatment with SNP, glyceryl trinitrate (GTN), and methylene blue (MB) in the acute KET animal...

  16. Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells

    OpenAIRE

    Volkov, Sergey; Vonk, Vedran; Khorshidi, Navid; Franz, Dirk; Kubicek, Markus; Kilic, Volkan; Felici, Roberto; Huber, Tobias M.; Navickas, Edvinas; Rupp, Ghislain M.; Fleig, Jürgen; Stierle, Andreas

    2016-01-01

    We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % y...

  17. Driven Morse Oscillator Model for Multi-photon Dissociation of Nitrogen Oxide

    CERN Document Server

    Ting, J J L

    1994-01-01

    Within a one-dimensional semi-classical model with a Morse potential the possibility of infrared multi-photon dissociation of vibrationally excited nitrogen oxide was studied. The dissociation thresholds of typical driving forces and couplings were found to be similar, which indicates that the results were robust to variations of the potential and of the definition of dissociation rate. PACS: 42.50.Hz, 33.80.Wz

  18. Kinetic Modelling for the Assay of Nortriptyline Hydrochloride Using Potassium Permanganate as Oxidant

    OpenAIRE

    Rahman, Nafisur; Khan, Sumaiya

    2014-01-01

    Kinetic methods for accurate determination of nortriptyline hydrochloride have been described. The methods are based on the oxidation of nortriptyline hydrochloride with KMnO4 in acidic and basic media. In acidic medium, the decrease in absorbance at 525.5 nm and in basic medium, the increase in absorbance at 608.5 nm were measured as a function of time. The variables affecting the reactions were carefully investigated and optimised. Kinetic models such as initial rate, rate constant, variabl...

  19. Recombinant human deoxyribonuclease attenuates oxidative stress in a model of eosinophilic pulmonary response in mice.

    Science.gov (United States)

    da Cunha, Aline Andrea; Nuñez, Nailê Karine; de Souza, Rodrigo Godinho; Vargas, Mauro Henrique Moraes; Silveira, Josiane Silva; Antunes, Géssica Luana; Schmitz, Felipe; de Souza Wyse, Angela Terezinha; Jones, Marcus Herbert; Pitrez, Paulo Márcio

    2016-02-01

    The inflammatory cells infiltrating the airways produce several mediators, such as reactive oxygen species (ROS). ROS and the oxidant-antioxidant imbalance might play an important role in the modulation of airways inflammation. In order to avoid the undesirable effects of ROS, various endogenous antioxidant strategies have evolved, incorporating both enzymatic and non-enzymatic mechanisms. Recombinant human deoxyribonuclease (rhDNase) in clinical studies demonstrated a reduction in sputum viscosity, cleaving extracellular DNA in the airways, and facilitating mucus clearance, but an antioxidant effect was not studied so far. Therefore, we evaluated whether the administration of rhDNase improves oxidative stress in a murine model of asthma. Mice were sensitized by two subcutaneous injections of ovalbumin (OVA), on days 0 and 7, followed by three lung challenges with OVA on days 14, 15, and 16. On days 15 and 16, after 2 h of the challenge with OVA, mice received 1 mg/mL of rhDNase in the lungs. Bronchoalveolar lavage fluid and lung tissue were obtained on day 17, for inflammatory and oxidative stress analysis. We showed that rhDNase did not alter the population of inflammatory cells, such as eosinophil cells, in OVA-treated rhDNase group but significantly improved oxidative stress in lung tissue, by decreasing oxygen reactive species and increasing superoxide dismutase/catalase ratio, glutathione peroxidase activity, and thiol content. Our data provide the first evidence that rhDNase decreases some measures of oxidative stress and antioxidant status in a murine model of asthma, with a potential antioxidant effect to be further studied in human asthma. PMID:26738487

  20. Observations and modeling of bromine induced mercury oxidation in the tropical free troposphere during TORERO

    Science.gov (United States)

    Coburn, Sean; Wang, Siyuan; terSchure, Arnout; Evans, Matt; Volkamer, Rainer

    2013-04-01

    The Tropical Ocean tRoposphere Exchange experiment TORERO (Jan/Feb 2012) probed air-sea exchange of very short lived halogens and organic carbon species over the full tropospheric air column above the eastern tropical Pacific Ocean. It is well known that halogens influence the oxidative capacity in the marine boundary layer, but their distribution and abundance is less clear in the tropical free troposphere, where most of tropospheric ozone mass resides, and about 80% of the global methane destruction occurs. The oxidation of elemental mercury (GEM) by halogens (i.e., bromine) further forms gaseous oxidized mercury (GOM), and this oxidation is accelerated at the low temperatures in the free troposphere compared to the boundary layer. Free tropospheric halogen radical abundances are thus of particular importance to understand the entry pathways for GOM deposition from the free troposphere to ecosystem, and the subsequent bio-accumulation of this neurotoxin. This presentation summarizes new observational evidence for halogen vertical distributions over the full tropospheric air column, and their abundance in the tropical troposphere, at mid-latitudes in the Northern and Southern hemisphere. BrO and IO were measured simultaneously by the CU Airborne MAX-DOAS instrument, and organic halogen precursors were measured by online GC-MS (TOGA) during 22 research flights aboard the NSF/NCAR GV aircraft. We employ atmospheric box modeling constrained by observations of gas-phase hydrocarbons, aerosols, photolysis frequencies, and meterological parameters measured aboard the plane to test the observed BrO and IO abundances, and evaluate the rate of GEM oxidation in light of recent updates about the stability of the Hg-Br adduct, and it's fate (Goodsite et al., 2012; Dibble et al., 2012). Finally, we compare our measurements with output from the GEOS-Chem model for selected case studies.

  1. 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

  2. The modeling of a standalone solid-oxide fuel cell auxiliary power unit

    Science.gov (United States)

    Lu, N.; Li, Q.; Sun, X.; Khaleel, M. A.

    In this research, a Simulink model of a standalone vehicular solid-oxide fuel cell (SOFC) auxiliary power unit (APU) is developed. The SOFC APU model consists of three major components: a controller model; a power electronics system model; and an SOFC plant model, including an SOFC stack module, two heat exchanger modules, and a combustor module. This paper discusses the development of the nonlinear dynamic models for the SOFC stacks, the heat exchangers and the combustors. When coupling with a controller model and a power electronic circuit model, the developed SOFC plant model is able to model the thermal dynamics and the electrochemical dynamics inside the SOFC APU components, as well as the transient responses to the electric loading changes. It has been shown that having such a model for the SOFC APU will help design engineers to adjust design parameters to optimize the performance. The modeling results of the SOFC APU heat-up stage and the output voltage response to a sudden load change are presented in this paper. The fuel flow regulation based on fuel utilization is also briefly discussed.

  3. Adsorption of Pentachlorophenol onto Oxide and Clay Minerals: Surface Reaction Model and Environmental Implications

    Institute of Scientific and Technical Information of China (English)

    WU Daqing; DIAO Guiyi; YUAN Peng; PENG Jinlian

    2006-01-01

    The adsorption of pentachlorophenol (PCP) onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH= 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation,meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmuir equation with the correlation coefficient R>0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order: hematite > lepidocrocite > goethite > kaolinite >quartz > montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.

  4. 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

    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...... on moving finite elements is used to solve the model equations. To our knowledge, this is the first serious attempt to model such transient systems in detail. The particle is divided into moving zones, described by the reaction between limestone and SO2, and each zone is assigned a certain catalytic...... 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...

  5. Modeling a full scale oxidation ditch system, coupling hydrodynamics and biological kinetics using ASM1 model

    International Nuclear Information System (INIS)

    Optimising the aeration in oxidation ditch aims on one hand, a better wastewater quality and on the other hand, a reduction of the energy expenses of the treatment. given that the energy expenses relative to the aeration represents 60 to 80% of the operating costs of a wastewater treatment plant and given that the biological activity is strictly dependent on dissolved oxygen, the transfer of oxygen is considered as one of the key parameters of the process. (Author) 8 refs.

  6. Melatonin Does Not Affect Oxidative/Inflammatory Biomarkers in a Closed-Chest Porcine Model of Acute Myocardial Infarction

    DEFF Research Database (Denmark)

    Halladin, Natalie L.; Ekelof, Sarah; Jensen, Svend Eggert;

    2014-01-01

    Aim: To test whether melatonin reduces oxidative and inflammatory biomarkers in a closed-chest porcine model of acute myocardial infarction. Materials and Methods: Twenty pigs were randomized to receive a total dosage of 200 mg (0.4 mg/ml) of melatonin, or placebo immediately prior to reperfusion...... or oxidative stress markers after experimental myocardial infarction compared to placebo....

  7. Therapeutic effects of hydrogen saturated saline on rat diabetic model and insulin resistant model via reduction of oxidative stress

    Institute of Scientific and Technical Information of China (English)

    WANG Qi-jin; ZHA Xiao-juan; KANG Zhi-min; XU Mao-jin; HUANG Qin; ZOU Da-jin

    2012-01-01

    Background Molecular hydrogen,as a novel antioxidant,has been proven effective in treating many diseases.This study aimed to evaluate the therapeutic effects of hydrogen saturated saline in treatment of a rat model of diabetes mellitus and a rat model of insulin resistant.Methods A rat diabetes mellitus model was established by feeding a high fat/high carbohydrate diet followed by injection of a small dose of streptozotocin,and an insulin resistant model was induced with a high glucose and high fat diet.Hydrogen saturated saline was administered to rats with both models conditions on a daily basis for eight weeks.A pioglitazone-treated group and normal saline-treated group served as positive and negative controls.The general condition,body weight,blood glucose,blood lipids,and serum insulin levels of rats were examined at the 8th week after treatment.The oxidative stress indices,including serum superoxide dismutase (SOD),glutathione (GSH) and malondialdehyde (MDA) were also evaluated after eight weeks of treatment using the commercial kits.Results Hydrogen saturated saline showed great efficiency in improving the insulin sensitivity and lowering blood glucose and lipids.Meanwhile,the therapeutic effects of hydrogen saturated saline were superior to those of pioglitazone.Hydrogen saturated saline markedly attenuated the MDA level and elevated the levels of antioxidants SOD and GSH.Conclusion Hydrogen saturated saline may improve the insulin resistance and alleviate the symptoms of diabetes mellitus by reducing the oxidative stress and enhancing the anti-oxidant system.

  8. 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.

  9. Numerical simulation of a combined oxidation ditch flow using 3D k-εturbulence model

    Institute of Scientific and Technical Information of China (English)

    LUO Lin; LI Wei-min; DENG Yong-sen; WANG Tao

    2005-01-01

    The standard three dimensional(3D) k-ε turbulence model was applied to simulate the flow field of a small scale combined oxidation ditch. The moving mesh approach was used to model the rotor of the ditch. Comparison of the computed and the measured data is acceptable. A vertical reverse flow zone in the ditch was found, and it played a very important role in the ditch flow behavior. The flow pattern in the ditch is discussed in detail, and approaches are suggested to improve the hydrodynamic performance in the ditch.

  10. Two-parameter stochastic resonance in a model of electrochemical oxidation of formic acid on Pt

    Institute of Scientific and Technical Information of China (English)

    皮宗新; 辛厚文

    2002-01-01

    Stochastic resonance (SR) is shown in a two-parameter system, a model of electro-chemical oxidation of formic acid on Pt. The driving current and the saturation coverage for carbon monoxide are two control parameters in this model. Modulation of an excitable focal stable state close to a Hopf bifurcation by a weak periodic signal in one parameter and noise in the other parameter is found to give rise to SR. The results indicate that the noise can enlarge a weak peri-odic signal and lead the system to be ordered. The scenario and novel aspects of SR in this system are discussed.

  11. Two-parameter stochastic resonance in a model of electrochemical oxidation of formic acid on Pt

    Institute of Scientific and Technical Information of China (English)

    皮宗新; 辛厚文

    2002-01-01

    Stochastic resonance (SR) is shown in a two-parameter system, a model of electrochemical oxidation of formic acid on Pt. The driving current and the saturation coverage for carbon monoxide are two control parameters in this model. Modulation of an excitable focal stable state close to a Hopf bifurcation by a weak periodic signal in one parameter and noise in the other parameter is found to give rise to SR. The results indicate that the noise can enlarge a weak periodic signal and lead the system to be ordered. The scenario and novel aspects of SR in this system are discussed.

  12. Sensitivity analysis for solid oxide fuel cells using a three-dimensional numerical model

    Energy Technology Data Exchange (ETDEWEB)

    Kapadia, S.; Anderson, W.K. [University of Tennessee SimCenter at Chattanooga, 701, East M.L. King Boulevard, Chattanooga, TN 37403 (United States)

    2009-04-15

    A three-dimensional numerical solver is developed to model complex transport processes inside all components of a solid oxide fuel cell (SOFC). An initial assessment of the accuracy of the model is made by comparing a numerically generated polarization curve with experimental results. Sensitivity derivatives of objective functions representing the cell voltage and the concentration polarization are obtained with respect to the material properties of the anode and the cathode using discrete adjoint method. Implementation of the discrete adjoint method is validated by comparing sensitivity derivatives obtained using the adjoint technique with results obtained using direct-differentiation and finite-difference methods. (author)

  13. Tungsten oxide in polymer electrolyte fuel cell electrodes-A thin-film model electrode study

    Energy Technology Data Exchange (ETDEWEB)

    Wickman, Bjoern, E-mail: bjorn.wickman@chalmers.s [Competence Centre for Catalysis, Department of Applied Physics, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden); Wesselmark, Maria; Lagergren, Carina; Lindbergh, Goeran [Applied Electrochemistry, School of Chemical Science and Engineering, KTH, SE-100 44 Stockholm (Sweden)

    2011-10-30

    Highlights: > Platinum and tungsten oxide thin-film electrocatalysts. > Single cell fuel cell evaluation. > Hydrogen-tungsten bronze formation. > CO oxidation on platinum on tungsten oxide. - Abstract: Thin films of WO{sub x} and Pt on WO{sub x} were evaporated onto the microporous layer of a gas diffusion layer (GDL) and served as model electrodes in the polymer electrolyte fuel cell (PEFC) as well as in liquid electrolyte measurements. In order to study the effects of introducing WO{sub x} in PEFC electrodes, precise amounts of WO{sub x} (films ranging from 0 to 40 nm) with or without a top layer of Pt (3 nm) were prepared. The structure of the thin-film model electrodes was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy prior to the electrochemical investigations. The electrodes were analyzed by cyclic voltammetry and the electrocatalytic activity for hydrogen oxidation reaction (HOR) and CO oxidation was examined. The impact of Nafion in the electrode structure was examined by comparing samples with and without Nafion solution sprayed onto the electrode. Fuel cell measurements showed an increased amount of hydrogen tungsten bronzes formed for increasing WO{sub x} thicknesses and that Pt affected the intercalation/deintercalation process, but not the total amount of bronzes. The oxidation of pre-adsorbed CO was shifted to lower potentials for WO{sub x} containing electrodes, suggesting that Pt-WO{sub x} is a more CO-tolerant catalyst than Pt. For the HOR, Pt on thicker films of WO{sub x} showed an increased limiting current, most likely originating from the increased electrochemically active surface area due to proton conductivity and hydrogen permeability in the WO{sub x} film. From measurements in liquid electrolyte it was seen that the system behaved very differently compared to the fuel cell measurements. This exemplifies the large differences between the liquid electrolyte and fuel cell systems. The thin-film model

  14. 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

    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...... strategies (periodic aeration vs. continuous aeration) reveals that periodic aeration can reduce NO and N2O production while maintaining a high level of nitrogen removal through promoting Anammox growth. Application of periodic aerations with different cycle frequencies to the MABR indicates that an increase......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...

  15. Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds

    Directory of Open Access Journals (Sweden)

    Lanjun Zhang

    2015-12-01

    Full Text Available This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30 °C to 80 °C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80 °C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO2 being released at 130 °C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS. The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What’s more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.

  16. Modeling Species Inhibition of NO Oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

    Energy Technology Data Exchange (ETDEWEB)

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Tran, Diana N.; Lee, Jong H.; Herling, Darrell R.

    2011-04-20

    Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ~ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the Fe-zeolite SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data. Such inhibition models will improve the accuracy of model based control design for integrated DPF-SCR aftertreatment systems.

  17. 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.

  18. Effect of Mannitol on Hyaluronic Acid Stability in Two in Vitro Models of Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Marguerite Rinaudo

    2014-07-01

    Full Text Available In this paper, we propose the evaluation of the mannitol’s ability to reduce hyaluronic acid (HA degradation using two different models of oxidative stress. Firstly, a solution of hyaluronan and a solution of the same HA including mannitol in PBS buffer were submitted to an oxidative stress generated by the addition of xanthine + xanthine oxidase generating oxygen free radicals. Different enzyme concentrations were used and the HA properties were studied after 24 h of contact at ambient temperature. Decreases of the viscosity of the solution were assessed by rheometry (viscous and elastic module and that of HA molecular weight was determined by steric exclusion chromatography. Rheologic behavior was assessed on identical HA solutions subjected to another model of oxidative stress imposed by addition of hydrogen peroxide. The influence of mannitol concentration on HA degradation was also demonstrated. Whatever the stress applied, it appears very clearly that mannitol protects hyaluronic acid from mediated oxygen free radicals degradation. These in vitro results suggest that mannitol could be a simple way to significantly increase the intra-articular residence time of the injected hyaluronic acid and therefore might improve viscosupplementation effectiveness.

  19. Proteomics-Based Metabolic Modeling Reveals That Fatty Acid Oxidation (FAO) Controls Endothelial Cell (EC) Permeability*

    Science.gov (United States)

    Patella, Francesca; Schug, Zachary T.; Persi, Erez; Neilson, Lisa J.; Erami, Zahra; Avanzato, Daniele; Maione, Federica; Hernandez-Fernaud, Juan R.; Mackay, Gillian; Zheng, Liang; Reid, Steven; Frezza, Christian; Giraudo, Enrico; Fiorio Pla, Alessandra; Anderson, Kurt; Ruppin, Eytan; Gottlieb, Eyal; Zanivan, Sara

    2015-01-01

    Endothelial cells (ECs) play a key role to maintain the functionality of blood vessels. Altered EC permeability causes severe impairment in vessel stability and is a hallmark of pathologies such as cancer and thrombosis. Integrating label-free quantitative proteomics data into genome-wide metabolic modeling, we built up a model that predicts the metabolic fluxes in ECs when cultured on a tridimensional matrix and organize into a vascular-like network. We discovered how fatty acid oxidation increases when ECs are assembled into a fully formed network that can be disrupted by inhibiting CPT1A, the fatty acid oxidation rate-limiting enzyme. Acute CPT1A inhibition reduces cellular ATP levels and oxygen consumption, which are restored by replenishing the tricarboxylic acid cycle. Remarkably, global phosphoproteomic changes measured upon acute CPT1A inhibition pinpointed altered calcium signaling. Indeed, CPT1A inhibition increases intracellular calcium oscillations. Finally, inhibiting CPT1A induces hyperpermeability in vitro and leakage of blood vessel in vivo, which were restored blocking calcium influx or replenishing the tricarboxylic acid cycle. Fatty acid oxidation emerges as central regulator of endothelial functions and blood vessel stability and druggable pathway to control pathological vascular permeability. PMID:25573745

  20. Real-world exposure of airborne particulate matter triggers oxidative stress in an animal model

    Science.gov (United States)

    Wan, Guohui; Rajagopalan, Sanjay; Sun, Qinghua; Zhang, Kezhong

    2010-01-01

    Epidemiological studies have shown a strong link between air pollution and the increase of cardio-pulmonary mortality and morbidity. In particular, inhaled airborne particulate matter (PM) exposure is closely associated with the pathogenesis of air pollution-induced systemic diseases. In this study, we exposed C57BIV6 mice to environmentally relevant PM in fine and ultra fine ranges (diameter < 2.5 μm, PM2.5) using a “real-world” airborne PM exposure system. We investigated the pathophysiologic impact of PM2.5 exposure in the animal model and in cultured primary pulmonary macrophages. We demonstrated that PM2.5 exposure increased the production of reactive oxygen species (ROS) in blood vessels in vivo. Furthermore, in vitro PM2.5 exposure experiment suggested that PM2.5 could trigger oxidative stress response, reflected by an increased expression of the anti-oxidative stress enzymes superoxide dismutase-1 (SOD-1) and heme oxygenase-1(HO-1), in mouse primary macrophages. Together, the results obtained through our “real-world” PM exposure approach demonstrated the pathophysiologic effect of ambient PM2.5 exposure on triggering oxidative stress in the specialized organ and cell type of an animal model. Our results and approach will be informative for the research in air pollution-associated physiology and pathology. PMID:21383899

  1. Kinetic modeling of native Cassava starch thermo-oxidative degradation using Weibull and Weibull-derived models.

    Science.gov (United States)

    Janković, Bojan

    2014-01-01

    A new approach in kinetic modeling of thermo-oxidative degradation process of starch granules extracted from the Cassava roots was developed. Based on the thermoanalytical measurements, three reaction stages were detected. Using Weibull and Weibull-derived (inverse) models, it was found that the first two reaction stages could be described with the change of apparent activation energy (Ea) on conversion fraction (α(T)) (using "Model-free" analysis). It was found that first reaction stage, which involves dehydration and evaporation of lower molecular mass fractions, can be described with an inverse Weibull model. This model with its distribution of Ea values and derived distribution parameters includes the occurrence of three-dimensional diffusion mechanism. The second reaction stage is very complex, and it was found to contain the system of simultaneous reactions (where depolymerization occurs), and can be described with standard Weibull model. Identified statistical model with its distribution of Ea values and derived distribution parameters includes the kinetic model that gives the variable reaction order values. Based on the established models, shelf-life studies for first two stages were carried out. Shelf-life testing has shown that optimal dehydration time is achieved by a programmed heating at medium heating rate, whereas optimal time of degradation is achieved at highest heating rate.

  2. 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.

  3. 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.

  4. Characterization of Solid Oxide Fuel Cell Components Using Electromagnetic Model-Based Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Zilberstein, Vladimir; Craven, Chris; Goldfine, Neil

    2004-12-28

    In this Phase I SBIR, the contractor demonstrated a number of capabilities of model-based sensors such as MWM sensors and MWM-Arrays. The key results include (1) porosity/microstructure characterization for anodes, (2) potential for cathode material characterization, (3) stress measurements in nickel and cobalt, and (4) potential for stress measurements in non-magnetic materials with a ferromagnetic layer. In addition, potential applications for manufacturing quality control of nonconductive layers using interdigitated electrode dielectrometers have been identified. The results indicate that JENTEK's MWM technology can be used to significantly reduce solid oxide fuel cell production and operating costs in a number of ways. Preliminary investigations of solid oxide fuel cell health monitoring and scale-up issues to address industry needs have also been performed.

  5. Effect of wall growth on the kinetic modeling of nitrite oxidation in a CSTR.

    Science.gov (United States)

    Dokianakis, Spiros N; Kornaros, Michael; Lyberatos, Gerasimos

    2006-03-01

    A simple kinetic model was developed for describing nitrite oxidation by autotrophic aerobic nitrifiers in a continuous stirred tank reactor (CSTR), in which mixed (suspended and attached) growth conditions prevail. The CSTR system was operated under conditions of constant nitrite feed concentration and varying volumetric flow rates. Experimental data from steady-state conditions in the CSTR system and from batch experiments were used for the determination of the model's kinetic parameters. Model predictions were verified against experimental data obtained under transient operating conditions, when volumetric flow rate and nitrite feed concentration disturbances were imposed on the CSTR. The presented kinetic modeling procedure is quite simple and general and therefore can also be applied to other mixed growth biological systems.

  6. Multi-scale Model of Residual Strength of 2D Plain Weave C/SiC Composites in Oxidation Atmosphere

    Science.gov (United States)

    Chen, Xihui; Sun, Zhigang; Sun, Jianfen; Song, Yingdong

    2016-06-01

    Multi-scale models play an important role in capturing the nonlinear response of woven carbon fiber reinforced ceramic matrix composites. In plain weave carbon fiber/silicon carbon (C/SiC) composites, the carbon fibers and interphases will be oxidized at elevated temperature and the strength of the composite will be degraded when oxygen enters micro-cracks formed in the as-produced parts due to the mismatch in thermal properties between constituents. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. In this paper, the change rule of fiber notch depth is fitted by circular function. And a multi-scale model based upon the change rule of fiber notch depth is developed to simulate the residual strength and post-oxidation stress-strain curves of the composite. The multi-scale model is able to accurately predict the residual strength and post-oxidation stress-strain curves of the composite. Besides, the simulated residual strength and post-oxidation stress-strain curves of 2D plain weave C/SiC composites in oxidation atmosphere show good agreements with experimental results. Furthermore, the oxidation time and temperature of the composite are investigated to show their influences upon the residual strength and post-oxidation stress-strain curves of plain weave C/SiC composites.

  7. 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

  8. Mathematical Modeling of Ammonia Electro-Oxidation on Polycrystalline Pt Deposited Electrodes

    Science.gov (United States)

    Diaz Aldana, Luis A.

    The ammonia electrolysis process has been proposed as a feasible way for electrochemical generation of fuel grade hydrogen (H2). Ammonia is identified as one of the most suitable energy carriers due to its high hydrogen density, and its safe and efficient distribution chain. Moreover, the fact that this process can be applied even at low ammonia concentration feedstock opens its application to wastewater treatment along with H 2 co-generation. In the ammonia electrolysis process, ammonia is electro-oxidized in the anode side to produce N2 while H2 is evolved from water reduction in the cathode. A thermodynamic energy requirement of just five percent of the energy used in hydrogen production from water electrolysis is expected from ammonia electrolysis. However, the absence of a complete understanding of the reaction mechanism and kinetics involved in the ammonia electro-oxidation has not yet allowed the full commercialization of this process. For that reason, a kinetic model that can be trusted in the design and scale up of the ammonia electrolyzer needs to be developed. This research focused on the elucidation of the reaction mechanism and kinetic parameters for the ammonia electro-oxidation. The definition of the most relevant elementary reactions steps was obtained through the parallel analysis of experimental data and the development of a mathematical model of the ammonia electro-oxidation in a well defined hydrodynamic system, such as the rotating disk electrode (RDE). Ammonia electro-oxidation to N 2 as final product was concluded to be a slow surface confined process where parallel reactions leading to the deactivation of the catalyst are present. Through the development of this work it was possible to define a reaction mechanism and values for the kinetic parameters for ammonia electro-oxidation that allow an accurate representation of the experimental observations on a RDE system. Additionally, the validity of the reaction mechanism and kinetic parameters

  9. Fuel/Oxidizer Injector Modeling in Sub- and Super-Critical Regimes for Deep Throttling Cryogenic Engines Project

    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...

  10. Thermodynamic Modeling of Oxide Phases in the Mn-O System

    Science.gov (United States)

    Kang, Youn-Bae; Jung, In-Ho

    2016-09-01

    A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Mn-O system are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25 °C) to above the liquidus temperature at compositions covering from MnO to MnO2, and oxygen partial pressure from 10-15 to 102 (bar). The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (α - and β -Mn3O4) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. Valence states of the spinels are interpreted based on the available thermopower measurement, for which Mn4+ was considered in the cubic spinel (β -Mn3O4). The present Mn3O4 spinel solutions can be integrated into a larger spinel solution database, which has been already developed. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram sections and thermodynamic properties.

  11. Mathematical modeling of an exothermic leaching reaction system: pressure oxidation of wide size arsenopyrite participates

    Science.gov (United States)

    Papangelakis, V. G.; Berk, D.; Demopoulos, G. P.

    1990-10-01

    In the design of processes involving exothermic reactions, as is the case of several sulfide leaching systems, it is desirable to utilize the energy liberated by the reaction to drive the reactor toward autogenous operation. For optimal reactor design, models which couple leaching kinetics and heat effects are needed. In this paper, the principles of modeling exothermic leaching reactions are outlined. The system investigated is the high-temperature (160 °C to 200 °C) pressure (O2) oxidation of arsenopyrite (FeAsS). The reaction system is characterized by three consecutive reactions: (1) heterogeneous dissolution of arsenopyrite particles, (2) homogeneous oxidation of iron(II) to iron(III), and (3) precipitation of scorodite (FeAsO4-2H2O). The overall kinetics is controlled by the arsenopyrite surface reaction. There was good agreement between laboratory-scale batch tests and model predictions. The model was expanded to simulate the performance of large-scale batch and single-stage continuous stirred tank reactor (CSTR) for the same rate-limiting regime. Emphasis is given to the identification of steady-state temperatures for autogenous processing. The effects of operating variables, such as feed temperature, slurry density, and retention time, on reactor operation and yield of leaching products are discussed.

  12. Thermodynamic Modeling of Oxide Phases in the Mn-O System

    Science.gov (United States)

    Kang, Youn-Bae; Jung, In-Ho

    2016-06-01

    A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Mn-O system are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25 °C) to above the liquidus temperature at compositions covering from MnO to MnO2, and oxygen partial pressure from 10-15 to 102 (bar). The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (α - and β -Mn3O4) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. Valence states of the spinels are interpreted based on the available thermopower measurement, for which Mn4+ was considered in the cubic spinel (β -Mn3O4). The present Mn3O4 spinel solutions can be integrated into a larger spinel solution database, which has been already developed. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram sections and thermodynamic properties.

  13. Lightning NOx Statistics Derived by NASA Lightning Nitrogen Oxides Model (LNOM) Data Analyses

    Science.gov (United States)

    Koshak, William; Peterson, Harold

    2013-01-01

    What is the LNOM? The NASA Marshall Space Flight Center (MSFC) Lightning Nitrogen Oxides Model (LNOM) [Koshak et al., 2009, 2010, 2011; Koshak and Peterson 2011, 2013] analyzes VHF Lightning Mapping Array (LMA) and National Lightning Detection Network(TradeMark) (NLDN) data to estimate the lightning nitrogen oxides (LNOx) produced by individual flashes. Figure 1 provides an overview of LNOM functionality. Benefits of LNOM: (1) Does away with unrealistic "vertical stick" lightning channel models for estimating LNOx; (2) Uses ground-based VHF data that maps out the true channel in space and time to < 100 m accuracy; (3) Therefore, true channel segment height (ambient air density) is used to compute LNOx; (4) True channel length is used! (typically tens of kilometers since channel has many branches and "wiggles"); (5) Distinction between ground and cloud flashes are made; (6) For ground flashes, actual peak current from NLDN used to compute NOx from lightning return stroke; (7) NOx computed for several other lightning discharge processes (based on Cooray et al., 2009 theory): (a) Hot core of stepped leaders and dart leaders, (b) Corona sheath of stepped leader, (c) K-change, (d) Continuing Currents, and (e) M-components; and (8) LNOM statistics (see later) can be used to parameterize LNOx production for regional air quality models (like CMAQ), and for global chemical transport models (like GEOS-Chem).

  14. Oxidative DNA damage background estimated by a system model of base excision repair

    Energy Technology Data Exchange (ETDEWEB)

    Sokhansanj, B A; Wilson, III, D M

    2004-05-13

    Human DNA can be damaged by natural metabolism through free radical production. It has been suggested that the equilibrium between innate damage and cellular DNA repair results in an oxidative DNA damage background that potentially contributes to disease and aging. Efforts to quantitatively characterize the human oxidative DNA damage background level based on measuring 8-oxoguanine lesions as a biomarker have led to estimates varying over 3-4 orders of magnitude, depending on the method of measurement. We applied a previously developed and validated quantitative pathway model of human DNA base excision repair, integrating experimentally determined endogenous damage rates and model parameters from multiple sources. Our estimates of at most 100 8-oxoguanine lesions per cell are consistent with the low end of data from biochemical and cell biology experiments, a result robust to model limitations and parameter variation. Our results show the power of quantitative system modeling to interpret composite experimental data and make biologically and physiologically relevant predictions for complex human DNA repair pathway mechanisms and capacity.

  15. A Review on Modeling of Hybrid Solid Oxide Fuel Cell Systems

    Directory of Open Access Journals (Sweden)

    Alan Fung

    2009-05-01

    Full Text Available Over the past 2 decades, there has been tremendous progress on numerical and computational tools for fuel cells and energy systems based on them. The purpose of this work is to summarize the current status of hybrid solid oxide fuel cell (SOFC cycles and identify areas that require further studies. In this review paper, a comprehensive literature survey on different types of SOFC hybrid systems modeling is presented. The paper has three parts. First, it describes the importance of the fuel cells modeling especially in SOFC hybrid cycles. Key features of the fuel cell models are highlighted and model selection criteria are explained. In the second part, the models in the open literature are categorized and discussed. It includes discussion on a detail example of SOFC-gas turbine cycle model, description of early models, models with different objectives such as parametric analysis, comparison of configurations, exergy analysis, optimization, non-stationary power generation applications, transient and off-design analysis, thermoeconomic analysis and so on. Finally, in the last section, key features of selected models are summarized and suggestions for areas that require further studies are presented. In this paper, a hybrid cycle can be any combination of SOFC and gas turbine, steam turbine, coal integrated gasification, and application in combined heat and power cycle.

  16. Polymerisation, basicity, oxidation state and their role in ionic modelling of silicate melts

    Directory of Open Access Journals (Sweden)

    R. Moretti

    2005-06-01

    Full Text Available In order to describe and quantify the reactivity of silicate melts, the ionic notation provided by the Temkin formalism has been historically accepted, giving rise to the study of melt chemical equilibria in terms of completely dissociated ionic species. Indeed, ionic modelling of melts works properly as long as the true extension of the anionic matrix is known. This information may be attained in the framework of the Toop-Samis (1962a,b model, through a parameterisation of the acid-base properties of the dissolved oxides. Moreover, by combining the polymeric model of Toop and Samis with the «group basicity» concept of Duffy and Ingram (1973, 1974a,b, 1976 the bulk optical basicity (Duffy and Ingram, 1971; Duffy, 1992 of molten silicates and glasses can be split into two distinct contributions, i.e. the basicity of the dissolved basic oxides and the basicity of the polymeric units. Application to practical cases, such as the assessment of the oxidation state of iron, require bridging of the energetic gap between the standard state of completely dissociated component (Temkin standard state and the standard state of pure melt component at P and T of interest. On this basis it is possible to set up a preliminary model for iron speciation in both anhydrous and hydrous aluminosilicate melts. In the case of hydrous melts, I introduce both acidic and basic dissociation of the water component, requiring the combined occurrence of H+ cations, OH- free anions and, to a very minor extent, of T-OH groups. The amphoteric behaviour of water revealed by this study is therefore in line with the earlier prediction of Fraser (1975.

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

    Science.gov (United States)

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

    2015-12-01

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

  18. 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

  19. Modelling and performance evaluation of solid oxide fuel cell for building integrated co- and polygeneration

    Energy Technology Data Exchange (ETDEWEB)

    Kazempoor, P. [Empa Swiss Federal Laboratories for Materials Science and Technology, Building Science and Technology Laboratory, Duebendorf (Switzerland); Mechanical Engineering Department, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Dorer, V. [Empa Swiss Federal Laboratories for Materials Science and Technology, Building Science and Technology Laboratory, Duebendorf (Switzerland); Ommi, F. [Mechanical Engineering Department, Tarbiat Modares University, Tehran (Iran, Islamic Republic of)

    2010-12-15

    Models of fuel cell based combined heat and power systems, used in building energy performance simulation codes, are often based on simple black or grey box models. To model a specific device, input data from experiments are often required for calibration. This paper presents an approach for the theoretical derivation of such data. A generic solid oxide fuel cell (SOFC) system model is described that is specifically developed for the evaluation of building integrated co- or polygeneration. First, a detailed computational cell model is developed for a planar SOFC and validated with available numerical and experimental data for intermediate and high temperature SOFCs with internal reforming (IT-DIR and HT-DIR). Results of sensitivity analyses on fuel utilisation and air excess ratio are given. Second, the cell model is extended to the stack model, considering stack pressure losses and the radiative heat transfer effect from the stack to the air flow. Third, two system designs based on the IT-DIR and HT-DIR SOFCs are modelled. Electric and CHP efficiencies are given for the two systems, as well as performance characteristics, to be used in simulations of building integrated co- and polygeneration systems. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. 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.

  1. Levels of oxidative stress parameters and the protective effects of melatonin in psychosis model rat testis

    Institute of Scientific and Technical Information of China (English)

    Bekir S.Parlaktas; Birsen Ozyurt; Huseyin Ozyurt; Ayten T.Tunc; Ali Akbas

    2008-01-01

    Aim: To evaluate the effects of melatonin on antioxidant enzyme levels and histopathologic changes in dizocilpine (MK-801)-induced psychosis model rat testis. Methods: A total of 24 adult male Wistar-Albino rats were divided into three groups with 8 in each. Group Ⅰ was used as control. Rats in Group Ⅱ were injected with MK-801 (0.5 mg/kg body weight i.p. for 5 days). In addition to MK-801, melatonin (50 mg/kg body weight i.p. once a day for 5 days) was injected into the rats in Group Ⅲ. The testes were harvested bilaterally for biochemical and histopathological examinations. Antioxidant enzyme activities, malondialdehyde, protein carbonyl and nitric oxide (NO) levels in tes-ticular tissues were analyzed using spectrophotometric analysis methods. Histopathological examinations of the testes were also performed. Results: MK-801 induced testicular damage, which resulted in significant oxidative stress (OS) by increasing the levels of antioxidant enzymes. The malondialdehyde, protein carbonyl and NO levels were increased in testicular tissues of rats. Treatment with melatonin led to significant decrease in oxidative injury.Administration of melatonin also reduced the detrimental histopathologic effects caused by MK-801. Conclusion:The results of the present study showed that MK-801 cause OS in testicular tissues of rats and treatment with melatonin can reduce the harmful effects of MK-801.

  2. Modelling of liquid metal flow and oxide film defects in filling of aluminium alloy castings

    Science.gov (United States)

    Dai, X.; Jolly, M.; Yang, X.; Campbell, J.

    2012-07-01

    The liquid metal flow behaviours in different runner system designs have important effects on the mechanical strength of aluminium alloy castings. In this paper, a new model has been developed which is a two-dimensional program using a finite difference technique and the Marker and Cell (MAC) method to simulate the flow of liquid metal during filling a mould. In the program the Eulerian method has been used for the liquid metal flow, while the Oxide Film Entrainment Tracking Algorithm (OFET) method (a Lagrangian method) has been used to simulate the movement of the oxide film on the liquid metal surface or in the liquid metal flow. Several examples have been simulated and tested and the relevant results were obtained. These results were compared with measured bending strengths. It was found that the completed program was capable of simulating effectively the filling processes of different runner systems. The simulation results are consistent with the experiment. In addition, the program is capable of providing clearer images for predicting the distribution of the oxide film defects generated during filling a mould.

  3. Impaired pulmonary artery contractile responses in a rat model of microgravity: role of nitric oxide

    Science.gov (United States)

    Nyhan, Daniel; Kim, Soonyul; Dunbar, Stacey; Li, Dechun; Shoukas, Artin; Berkowitz, Dan E.

    2002-01-01

    Vascular contractile hyporesponsiveness is an important mechanism underlying orthostatic intolerance after microgravity. Baroreceptor reflexes can modulate both pulmonary resistance and capacitance function and thus cardiac output. We hypothesized, therefore, that pulmonary vasoreactivity is impaired in the hindlimb-unweighted (HLU) rat model of microgravity. Pulmonary artery (PA) contractile responses to phenylephrine (PE) and U-46619 (U4) were significantly decreased in the PAs from HLU vs. control (C) animals. N(G)-nitro-L-arginine methyl ester (10(-5) M) enhanced the contractile responses in the PA rings from both C and HLU animals and completely abolished the differential responses to PE and U4 in HLU vs. C animals. Vasorelaxant responses to ACh were significantly enhanced in PA rings from HLU rats compared with C. Moreover, vasorelaxant responses to sodium nitroprusside were also significantly enhanced. Endothelial nitric oxide synthase (eNOS) and soluble guanlyl cyclase expression were significantly enhanced in PA and lung tissue from HLU rats. In marked contrast, the expression of inducible nitric oxide synthase was unchanged in lung tissue. These data support the hypothesis that vascular contractile responsiveness is attenuated in PAs from HLU rats and that this hyporesponsiveness is due at least in part to increased nitric oxide synthase activity resulting from enhanced eNOS expression. These findings may have important implications for blood volume distribution and attenuated stroke volume responses to orthostatic stress after microgravity exposure.

  4. Thermodynamic database development-modeling and phase diagram calculations in oxide systems

    Institute of Scientific and Technical Information of China (English)

    Arthur D. Pelton

    2006-01-01

    The databases of the FactSage thermodynamic computer system have been under development for 30 years. These databases contain critically evaluated and optimized data for thousands of compounds and hundreds of multicomponent solutions of solid and liquid metals, oxides, salts, sulfides, etc. The databases are automatically accessed by user-friendly software that calculates complex multiphase equilibria in large multicomponent systems for a wide variety of possible input/output constraints. The databases for solutions have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for different types of solutions involving sublattices, ordering, etc. Through the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits and permit extrapolation into regions of temperature and composition where data are unavailable. The present article focuses on the databases for solid and liquid oxide phases involving 25 elements. A short review of the available databases is presented along with the models used for the molten slag and the solid solutions such as spinel, pyroxene, olivine, monoxide, corundum, etc. The critical evaluation/optimization procedure is outlined using examples from the A12O3-SiO2-CaO-FeO-Fe2O3 system. Sample calculations are presented in which the oxide databases are used in conjunction with the FactSage databases for metallic and other phases. In particular, the use of the FactSage module for the calculation of multicomponent phase diagrams is illustrated.

  5. Paricalcitol may improve oxidative DNA damage on experimental amikacin-induced nephrotoxicity model.

    Science.gov (United States)

    Bulut, Gulay; Basbugan, Yildiray; Ari, Elif; Erten, Remzi; Bektas, Havva; Alp, Hamit Hakan; Bayram, Irfan

    2016-06-01

    This study aimed to investigate the possible protective effect of paricalcitol on experimental amikacin-induced nephrotoxicity model in rats. Wistar albino rats (n = 32) were allocated into four equal groups of eight each, the control (Group C), paricalcitol (Group P), amikacin-induced nephrotoxicity (Group A), and paricalcitol-treated amikacin-induced nephrotoxicity (Group A + P) groups. Paricalcitol was given intra-peritoneally at a dose of 0.4 μg/kg/d for 5 consecutive days prior to induction of amikacin-induced nephrotoxicity. Intra-peritoneal amikacin (1.2 g/kg) was used to induce nephrotoxicity at day 4. Renal function parameters, oxidative stress biomarkers, oxidative DNA damage (8-hydroxy-2'-deoxyguanosine/deoxyguanosine ratio), kidney histology, and vascular endothelial growth factor (VEGF) immunoexpression were determined. Group A + P had lower mean fractional sodium excretion (p deoxyguanosine/deoxyguanosine ratio (8-OHdG/dG ratio) (p < 0.001) were significantly lower; superoxide dismutase (p = 0.024) and glutathione peroxidase (p = 0.007) activities of renal tissue were significantly higher in group A + P than in group A. The mean scores of tubular necrosis (p = 0.024), proteinaceous casts (p = 0.038), medullary congestion (p = 0.035), and VEGF immunoexpression (p = 0.018) were also lower in group A + P when compared with group A. This study demonstrates the protective effect of paricalcitol in the prevention of amikacin-induced nephrotoxicity in an experimental model. Furthermore, it is the first study to demonstrate that paricalcitol improves oxidative DNA damage in an experimental acute kidney injury model. PMID:26983906

  6. Experimental and model analysis of the co-oxidative behavior of syngas feed in an Intermediate Temperature Solid Oxide Fuel Cell

    Science.gov (United States)

    Donazzi, A.; Rahmanipour, M.; Maestri, M.; Groppi, G.; Bardini, L.; Pappacena, A.; Boaro, M.

    2016-02-01

    By means of model analysis, we show that, in the presence of syngas, the electro-oxidation of H2 and that of CO occur in parallel and contemporarily on Samaria-doped Ceria (Sm0.2Ce0.8O1.9, SDC) Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFCs). The activation of a co-oxidative route is a most distinguishing feature of Ce-based cells, compared to traditional SOFCs. SDC electrolyte supported IT-SOFCs with Cu-Pd-CZ80 composite anodes and LSCF cathodes were tested under a wide range of operating conditions. Polarization and EIS measurements were collected at 600 °C and 650 °C with syngas mixtures (2.3-0.4H2/CO ratio), H2/N2 mixtures (from 97 to 30% H2 v/v) and CO/CO2 mixtures (from 97 to 50% CO v/v). A 1D, dynamic and heterogeneous model of the cell was applied to analyze the polarization and the EIS curves. The kinetics of the reactions of H2 electro-oxidation, CO electro-oxidation and O2 reduction were individually investigated and global power law rates were derived. The syngas experiments were simulated on a fully predictive basis and no parameter adjustment, confirming that the polarization behavior could be best reproduced exclusively by assuming the presence of the co-oxidative route. The IT-SOFCs were also exposed to biogas mixtures, revealing that the dry-reforming reaction was active.

  7. Reactive magnesium oxide cements: geochemical modelling of pH profile and solid phase composition

    International Nuclear Information System (INIS)

    Due to a range of technical and sustainability advantages, reactive magnesium oxide cements (MgO) are a potential alternative to Portland cement (PC) for conditioning intermediate level radioactive waste (ILW). MgO cements consist of a mixture of hydraulic cement and reactive magnesium oxide to which pozzolans such as silica fume (SF) may be added. While favourable, the mechanical and chemical properties of MgO matrices still require further investigation to ensure effective immobilisation of contaminants. In this study a solubility-speciation model was developed using PHREEQC to simulate blends based on low and high contents of MgO, including SF as a supplementary material. Analyses aimed at characterising binding systems focusing on their equilibrium pH with pure water and saturation index (SI) of solid phases. The geochemical model successfully confirmed that the equilibrium pH is inversely proportional to the fraction of MgO and SF present in the hydrated paste. Comparison with data available on literature mostly gave a consistent picture and the model provided reasonable predictions of existent solid phases. (authors)

  8. Compositional Fragmentation Model for the Oxidation of Sulfide Particles in a Flash Reactor

    Science.gov (United States)

    Parra-Sánchez, Víctor Roberto; Pérez-Tello, Manuel; Duarte-Ruiz, Cirilo Andrés; Sohn, Hong Yong

    2014-04-01

    A mathematical model to predict the size distribution and chemical composition of a cloud of sulfide particles during high-temperature oxidation in a flash reactor is presented. The model incorporates the expansion and further fragmentation of the reacting particles along their trajectories throughout the reaction chamber. A relevant feature of the present formulation is its flexibility to treat a variety of flash reacting systems, such as the flash smelting and flash converting processes. This is accomplished by computing the chemical composition of individual particles and the size distribution and overall composition of the particle cloud in separate modules, which are coupled through a database of particle properties previously stored on disk. The flash converting of solid copper mattes is considered as an example. The model predictions showed good agreement with the experimental data collected in a large laboratory reactor in terms of particle size distribution and sulfur remaining in the population of particles. The cumulative contribution and distribution coefficients are introduced to quantify the relationship between specific particle sizes in the feed and those in the reacted products upon oxidation, the latter of which has practical implications on the amount and chemical composition of dust particles produced during the industrial operation.

  9. 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

    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...... 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...... the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C2H4 are more complex than those prevailing...

  10. 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...... 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...... strategies to improve operation performance and to meet the new plant performance criteria such as minimization of greenhouse gas (in particular of nitrous oxide) emissions....

  11. 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.

  12. Modelling the growth of methane-oxidizing bacteria in a fixed biofilm

    DEFF Research Database (Denmark)

    Bilbo, Carl Morten; Arvin, Erik; Holst, Helle;

    1992-01-01

    Methane-oxidizing bacteria were grown in a fixed biofilm reactor in order to study their ability to degrade chlorinated aliphatic hydrocarbons. Focus is on the growth behaviour of the mixed culture. The growth is described by a model that includes methanotrophic bacteria in the active biomass....... The study forms the basis for setting up a future meauring programme. This work indicates a yield coefficient for methanotrophs of 0.36 mg biomass COD per mg CH$-4$/. In weight units this corresponds to approx. 1.44 mg biomass per mg CH$-4$/. This is close to the theoretical maximum growth yield...

  13. Evaluation of the mitochondrial respiratory chain and oxidative phosphorylation system using yeast models of OXPHOS deficiencies.

    Science.gov (United States)

    Fontanesi, Flavia; Diaz, Francisca; Barrientos, Antoni

    2009-10-01

    The oxidative phosphorylation (OXPHOS) system consists of five multimeric complexes embedded in the mitochondrial inner membrane. They work in concert to drive the aerobic synthesis of ATP. Mitochondrial and nuclear DNA mutations affecting the accumulation and function of these enzymes are the most common cause of mitochondrial diseases and have also been associated with neurodegeneration and aging. Several approaches for the assessment of the OXPHOS system enzymes have been developed. Based on the methods described elsewhere, this unit describes the creation and study of yeast models of mitochondrial OXPHOS deficiencies.

  14. Evidence of oxidative injury during aging of the liver in a mouse model.

    OpenAIRE

    Colantoni, Alessandra; Idilman, Ramazan; De Maria, Nicola; Duffner, Lisa A.; VAN THIEL, DAVID H.; Witte, Pamela L.; Kovacs, Elizabeth J.

    2001-01-01

    The aim of the present study was to determine whether oxidative stress contributes to aging of the liver in a mouse model. Liver was obtained from young (3–5 months old) and aged (18–24 months old) mice. No age-induced gross changes in liver morphology were detected by light microscopy. Apoptosis was measured using the fragment end labeling of DNA for the immunohistochemical identification of the apoptotic nuclei. The total apoptotic cells represented 1% of the total cells in livers of young ...

  15. Experimental and Kinetic Modeling Study of C2H2Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Tihic; Hashemi, Hamid;

    2016-01-01

    A detailed chemical kinetic model for oxidation of acetylene at intermediate temperatures and high pressure has been developed and evaluated experimentally. The rate coefficients for the reactions of C2H2 with HO2 and O2 were investigated, based on the recent analysis of the potential energy...... to be more than 50 kcal mol−1 and predictions of the initiation temperature were not sensitive to this reaction. Experiments were conducted with C2H2/O2 mixtures highly diluted in N2 in a high-pressure flow reactor at 600–900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel...

  16. Ability of silybin and its derivatives to prevent protein oxidation in different model systems

    DEFF Research Database (Denmark)

    Purchartová, K.; Baron, C.P.; Křen, V.

    2013-01-01

    to prevent activation of hemoglobin (Hb) to highly reactive hypervalent heme protein species (ferrylHb and perferrylHb) was examined. Indeed, Hb cytotoxicity has been associated with the generation of protein radicals, which are formed when the ferric iron of Hb (Fe3+) is oxidised by H2O2 to (Fe4......+) to form perferrylHb and ferrylHb, with the later also bearing a radical on its protein. The relationship between the structural properties of silybin and its derivatives and their ability to prevent oxidation of Hb was investigated in model system in the presence or the absence of lipids. The...... protein species....

  17. Measurement-based modelling of bromine-induced oxidation of mercury above the Dead Sea

    Directory of Open Access Journals (Sweden)

    E. Tas

    2012-03-01

    Full Text Available Atmospheric mercury depletion events (AMDEs outside the polar region – driven by high levels of gaseous Br and BrO (i.e., BrOx – were observed recently in the warm Dead Sea boundary layer. The efficient oxidation of gaseous elemental mercury (GEM under temperate conditions by BrOx was unexpected considering that the thermal back dissociation reaction of HgBr is about 2.5 orders of magnitude higher under Dead Sea temperatures compared to polar temperatures, and hence was expected to significantly slow down GEM oxidation under warm temperatures. The goal of this modelling study was to improve understanding of the interaction of reactive bromine and mercury during Dead Sea AMDEs using numerical simulations based on a comprehensive measurement campaign in summer 2009.

    Our analysis is focused on daytime AMDE when chemical processes dominate concentration changes. Best agreements between simulations and observations were achieved using rate constants for kHg+Br and kHg+BrO of 2.7 × 10−13 cm3 molecule−1 s−1 and 1.5 × 10−13 cm3 molecule−1 s−1, respectively. Our model also predicted that a rate constant kHg+BrO of 5.0 × 10−14 cm3 molecule−1 s−1 may be considered as a minimum, which is higher than most reported values. These rate constants suggest that BrO could be a more efficient oxidant than Br in the troposphere as long as [Br]/[BrO] ratios are smaller than ~0.2 to 0.5. Under Dead Sea conditions, these kinetics demonstrate a high efficiency and central role of BrOx for AMDEs, with relative contributions to GEM depletion of more than ~90%. Unexpectedly, BrO was found to be the dominant oxidant with relative contributions above 80%. The strong contribution of BrO could explain why the efficiency of GEM

  18. Comprehensive Assessment of Oxidatively Induced Modifications of DNA in a Rat Model of Human Wilson's Disease.

    Science.gov (United States)

    Yu, Yang; Guerrero, Candace R; Liu, Shuo; Amato, Nicholas J; Sharma, Yogeshwar; Gupta, Sanjeev; Wang, Yinsheng

    2016-03-01

    Defective copper excretion from hepatocytes in Wilson's disease causes accumulation of copper ions with increased generation of reactive oxygen species via the Fenton-type reaction. Here we developed a nanoflow liquid chromatography-nanoelectrospray ionization-tandem mass spectrometry coupled with the isotope-dilution method for the simultaneous quantification of oxidatively induced DNA modifications. This method enabled measurement, in microgram quantities of DNA, of four oxidative stress-induced lesions, including direct ROS-induced purine cyclonucleosides (cPus) and two exocyclic adducts induced by byproducts of lipid peroxidation, i.e. 1,N(6)-etheno-2'-deoxyadenosine (εdA) and 1,N(2)-etheno-2'-deoxyguanosine (εdG). Analysis of liver tissues of Long-Evans Cinnamon rats, which constitute an animal model of human Wilson's disease, and their healthy counterparts [i.e. Long-Evans Agouti rats] showed significantly higher levels of all four DNA lesions in Long-Evans Cinnamon than Long-Evans Agouti rats. Moreover, cPus were present at much higher levels than εdA and εdG lesions. In contrast, the level of 5-hydroxymethyl-2'-deoxycytidine (5-HmdC), an oxidation product of 5-methyl-2'-deoxycytidine (5-mdC), was markedly lower in the liver tissues of Long-Evans Cinnamon than Long-Evans Agouti rats, though no differences were observed for the levels of 5-mdC. In vitro biochemical assay showed that Cu(2+) ions could directly inhibit the activity of Tet enzymes. Together, these results suggest that aberrant copper accumulation may perturb genomic stability by elevating oxidatively induced DNA lesions, and by altering epigenetic pathways of gene regulation.

  19. An experimental and kinetic modeling study of the oxidation of the four isomers of butanol.

    Science.gov (United States)

    Moss, Jeffrey T; Berkowitz, Andrew M; Oehlschlaeger, Matthew A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

    2008-10-30

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock-tube measurements. Reaction flux and sensitivity analysis illustrates the relative importance of the three competing classes of consumption reactions during the oxidation of the four butanol isomers: dehydration, unimolecular decomposition, and H-atom abstraction. Kinetic modeling indicates that the consumption of 1-butanol and iso-butanol, the most reactive isomers, takes place primarily by H-atom abstraction resulting in the formation of radicals, the decomposition of which yields highly reactive branching agents, H atoms and OH radicals. Conversely, the consumption of tert-butanol and 2-butanol, the least reactive isomers, takes place primarily via dehydration, resulting in the formation of alkenes, which lead to resonance stabilized radicals with very low reactivity. To our knowledge, the ignition-delay measurements and oxidation mechanism presented here for 2-butanol, iso-butanol, and tert-butanol are the first of their kind.

  20. Comprehensive Assessment of Oxidatively Induced Modifications of DNA in a Rat Model of Human Wilson's Disease.

    Science.gov (United States)

    Yu, Yang; Guerrero, Candace R; Liu, Shuo; Amato, Nicholas J; Sharma, Yogeshwar; Gupta, Sanjeev; Wang, Yinsheng

    2016-03-01

    Defective copper excretion from hepatocytes in Wilson's disease causes accumulation of copper ions with increased generation of reactive oxygen species via the Fenton-type reaction. Here we developed a nanoflow liquid chromatography-nanoelectrospray ionization-tandem mass spectrometry coupled with the isotope-dilution method for the simultaneous quantification of oxidatively induced DNA modifications. This method enabled measurement, in microgram quantities of DNA, of four oxidative stress-induced lesions, including direct ROS-induced purine cyclonucleosides (cPus) and two exocyclic adducts induced by byproducts of lipid peroxidation, i.e. 1,N(6)-etheno-2'-deoxyadenosine (εdA) and 1,N(2)-etheno-2'-deoxyguanosine (εdG). Analysis of liver tissues of Long-Evans Cinnamon rats, which constitute an animal model of human Wilson's disease, and their healthy counterparts [i.e. Long-Evans Agouti rats] showed significantly higher levels of all four DNA lesions in Long-Evans Cinnamon than Long-Evans Agouti rats. Moreover, cPus were present at much higher levels than εdA and εdG lesions. In contrast, the level of 5-hydroxymethyl-2'-deoxycytidine (5-HmdC), an oxidation product of 5-methyl-2'-deoxycytidine (5-mdC), was markedly lower in the liver tissues of Long-Evans Cinnamon than Long-Evans Agouti rats, though no differences were observed for the levels of 5-mdC. In vitro biochemical assay showed that Cu(2+) ions could directly inhibit the activity of Tet enzymes. Together, these results suggest that aberrant copper accumulation may perturb genomic stability by elevating oxidatively induced DNA lesions, and by altering epigenetic pathways of gene regulation. PMID:26362317

  1. Process-Scale Modeling of Atmosphere-Snowpack Exchange of Nitrogen Oxides

    Science.gov (United States)

    Murray, K. A.; Doskey, P. V.; Ganzeveld, L.

    2013-12-01

    Snowpack over glacial ice is a reservoir for reactive nitrogen gases. Previous studies indicate nitrogen oxides (NOx) are generated in snowpack interstitial air through photolysis of nitrate (NO3-). Gradients in NOx mixing ratios between snowpack interstitial air and the overlying atmosphere regulate exchange of NOx with snowpack, which affects the Arctic ozone budget and climate. To better understand the dynamics of cryosphere-atmosphere exchange of NOx in the Arctic, we collected 2 years of meteorological and chemical data in and above the snowpack at Summit, Greenland. The comprehensive dataset indicates NOx emissions are episodic, with NOx enhancements in snowpack in early spring during high wind speed events (10-20 mph), which elevate NOx levels to ~500 pptv at depths of 2.5 m. Analysis of the observations will be based upon application of a 1-D process-scale model of atmosphere-snowpack exchange of NOx. The model will include representations of the snowpack chemistry in gas and aqueous phases, mass transfer of chemical species between phases, and physical transport by diffusion and wind pumping. The model will calculate the chemical and physical tendencies in three dimensions: depth, time, and intensity. Analysis of the tendencies will allow us to perform model sensitivity tests of pertinent snowpack physical and chemical processes. The end-goal of the project is to simplify the major tendencies into a parameterized model add-on for use in global models to determine the importance of properly representing snowpack in global model simulations.

  2. 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

    2016-01-01

    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. PMID:27125491

  3. 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

    2016-01-01

    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. PMID:27125491

  4. Selective oxidation of sulfurs and oxidation desulfurization of model oil by 12-tungstophosphoric acid on cobalt-ferrite nanoparticles as magnetically recoverable catalyst

    Institute of Scientific and Technical Information of China (English)

    Ezzat Rafiee; Nasibeh Rahpeyma

    2015-01-01

    Silica-coated CoFe2O4 nanoparticles were prepared and used as a support for the immobilization of 12-tungstophosphoric acid, to produce a new magnetically separable catalyst. This catalyst was characterized using X-ray diffraction, wavelength-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, laser par-ticle size analysis, and vibrating sample magnetometry. The catalyst showed high activity in the selective oxidation of thioethers and thiophenes to the corresponding sulfones under mild condi-tions. The catalytic activity of the nanocatalyst in the oxidative desulfurization of model oil was investigated. The effect of nitrogen-containing compounds on sulfur removal from the model oil was also evaluated. The catalyst showed high activity in the oxidative desulfurization of diesel. The cata-lyst can be readily isolated from the oxidation system using an external magnet and no obvious loss of activity was observed when the catalyst was reused in four consecutive runs.

  5. Experimental study and modelling of the high temperature mechanical behavior of oxide dispersion strengthened ferritic steels

    International Nuclear Information System (INIS)

    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 Y2O3 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)

  6. Three-dimensional three-phase model for simulation of hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification in an oxidation ditch.

    Science.gov (United States)

    Lei, Li; Ni, Jinren

    2014-04-15

    A three-dimensional three-phase fluid model, supplemented by laboratory data, was developed to simulate the hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification processes in an oxidation ditch. The model provided detailed phase information on the liquid flow field, gas hold-up distribution and sludge sedimentation. The three-phase model described water-gas, water-sludge and gas-sludge interactions. Activated sludge was taken to be in a pseudo-solid phase, comprising an initially separated solid phase that was transported and later underwent biological reactions with the surrounding liquidmedia. Floc parameters were modified to improve the sludge viscosity, sludge density, oxygen mass transfer rate, and carbon substrate uptake due to adsorption onto the activated sludge. The validation test results were in very satisfactory agreement with laboratory data on the behavior of activated sludge in an oxidation ditch. By coupling species transport and biological process models, reasonable predictions are made of: (1) the biochemical kinetics of dissolved oxygen, chemical oxygen demand (COD) and nitrogen variation, and (2) the physical kinematics of sludge sedimentation.

  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

    2016-01-01

    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 R(2) 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. PMID:27622593

  8. 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.

  9. Numerical modelling of methane-powered micro-tubular, single-chamber solid oxide fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Akhtar, N. [School of Applied Mathematics, University of Birmingham, B15 2TT (United Kingdom); Department of Chemical Engineering, University of Birmingham, B15 2TT (United Kingdom); Decent, S.P. [School of Applied Mathematics, University of Birmingham, B15 2TT (United Kingdom); Kendall, K. [Department of Chemical Engineering, University of Birmingham, B15 2TT (United Kingdom)

    2010-12-01

    An experimentally validated, two-dimensional, axisymmetric, numerical model of micro-tubular, single-chamber solid oxide fuel cell (MT-SC-SOFC) has been developed. The model incorporates methane full combustion, steam reforming, dry reforming and water-gas shift reaction followed by electrochemical oxidation of produced hydrogen within the anode. On the cathode side, parasitic combustion of methane along with the electrochemical oxygen reduction is implemented. The results show that the poor performance of single-chamber SOFC as compared to the conventional (dual-chamber) SOFC (in case of micro-tubes) is due to the mass transport limitation on the anode side. The gas velocity inside the micro-tube is far too low when compared to the gas-chamber inlet velocity. The electronic current density is also non-uniform over the cell length, mainly due to the short length of the anode current collector located at the cell outlet. Furthermore, the higher temperature near the cell edges is due to the methane combustion (very close to the cell inlet) and current collection point (at the cell outlet). Both of these locations could be sensitive to the silver current collecting wire as silver may rupture due to cell overheating. (author)

  10. A DFT study of phenol adsorption on a low doping Mn-Ce composite oxide model

    Science.gov (United States)

    D´Alessandro, Oriana; Pintos, Delfina García; Juan, Alfredo; Irigoyen, Beatriz; Sambeth, Jorge

    2015-12-01

    Density functional theory calculations (DFT + U) were performed on a low doping Mn-Ce composite oxide prepared from experimental data, including X-ray diffraction (XRD) and temperature-programmed reduction (TPR). We considered a 12.5% Mn-doped CeO2 solid solution with fluorite-type structure, where Mn replaces Ce4+ leading to an oxygen-deficient bulk structure. Then, we modeled the adsorption of phenol on the bare Ce0.875Mn0.125O1.9375(1 1 1) surface. We also studied the effect of water adsorption and dissociation on phenol adsorption on this surface, and compared the predictions of DFT + U calculations with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements. The experimental results allowed us to both build a realistic model of the low doping Mn-Ce composite oxide and support the prediction that phenol is adsorbed as a phenoxy group with a tilt angle of about 70° with respect to the surface.

  11. 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.

  12. 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.

  13. 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.)

  14. Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

    International Nuclear Information System (INIS)

    During summertime high pressure conditions, high photo-oxidant (O3, H2O2, 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, NOx, 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 O3, H2O2 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 NOx-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 NOx-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 NOx-reduction scenario alone. (author) figs., tabs., 75 refs

  15. 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. PMID:26073590

  16. 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...... 2 OH ⇌ CH 2O+H, CH 3O⇌ CH 2O+H, CH 3O⇌ CH 2 OH , and CH 3O+O2⇌ CH 2O+ HO 2. The experiments, involving CH3OH/O2 mixtures diluted in N2, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under...... generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH3OH under the investigated conditions were very similar to those prevailing at higher temperatures...

  17. Cyclobutyl methyl ketone as a model compound for pinonic acid to elucidate oxidation mechanisms

    Directory of Open Access Journals (Sweden)

    A. P. Praplan

    2012-04-01

    Full Text Available 3-Methyl-1,2,3-tricarboxylic acid (MBTCA, terpenylic acid and diaterpenylic acid acetate were identified in secondary organic aerosol (SOA from α-pinene photooxidation or ozonolysis. These compounds display interesting structural features: MBTCA has a high oxygen to carbon ratio, terpenylic acid contains a lactone ring in its structure and diaterpenylic acid acetate possesses an ester functional group. The reaction mechanisms leading to these products are still unknown, but it was demonstrated experimentally in earlier studies that MBTCA is formed from pinonic acid, a primary ozonolysis product of α-pinene. Because the direct observation of pinonic acid oxidation in a smog chamber would be difficult due to its relatively low volatility, a model compound possessing the substructure of interest was used instead: cyclobutyl methyl ketone (CMK. From its oxidation, several organic acids could be measured with ion chromatography (IC coupled to a mass spectrometer (MS. Succinic acid, the analogous product of MBTCA is formed at molar yields of 2 to 5%. Butyrolactone is detected as butanoic acid, due to hydrolysis in the sampling device. A monocarboxylic acid with nominal mass 146 was detected in the absence of nitrogen oxides (NOx and could be the analogous product of diaterpenylic acid acetate. However, due to a lack of available standards, the exact structure of this compound remains unelucidated. Finally, 4-oxobutanoic acid could also be measured and two structures of its expected analogous compound from pinonic acid oxidation are proposed. Because these compounds are primary products of the CMK oxidation, reaction mechanisms capable of adding one or two carboxylic functional groups without formation of stable intermediate products needs to be formulated. Such a formation mechanism of MBTCA from pinonic acid was found in the literature; however, it includes a hydrogen atom migration to an acyloxy radical, which is expected to loose

  18. Comparison between two methane reforming models applied to a quasi-two-dimensional planar solid oxide fuel cell model

    International Nuclear Information System (INIS)

    Up to recently 2-D solid oxide fuel cell (SOFC) modelling efforts were based on global kinetic approaches for the methane steam reforming and water gas shift reactions (WGS) or thermodynamic equilibrium. Lately detailed models for elementary heterogeneous chemical kinetics of reforming (HCR) over Ni-YSZ anode became available in literature. Both approaches were employed in a quasi 2-D model of a planar high temperature electrolyte supported (ESC) SOFC and simulations were carried out for three different fuel gas compositions: pre-reformed natural gas (high CH4 content), and two different biomass derived producer gases (low CH4 content). The results show that the HCR predicts much slower reforming rates which leads to a more evenly distributed solid temperature but smaller power output and thus electrical efficiency. The two models result into predictions that differ greatly if high methane content fuels are used and for such cases the decision upon the modelling scheme to follow should be based on experimental investigations.

  19. Modeling the Effect of Oxidation on Tensile Strength of Carbon Fiber-Reinforced Ceramic-Matrix Composites

    Science.gov (United States)

    Longbiao, Li

    2015-12-01

    An analytical method has been developed to investigate the effect of oxidation on the tensile strength of carbon fiber - reinforced ceramic - matrix composites (CMCs). The Budiansky - Hutchinson - Evans shear - lag model was used to describe the micro stress field of the damaged composite considering fibers failure. The statistical matrix multicracking model and fracture mechanics interface debonding criterion were used to determine the matrix crack spacing and interface debonded length. The fiber strength degradation model and oxidation region propagation model have been adopted to analyze the oxidation effect on tensile strength of the composite, which is controlled by diffusion of oxygen gas through matrix cracks. Under tensile loading, the fibers failure probabilities were determined by combining oxidation model and fiber statistical failure model based on the assumption that fiber strength is subjected to two-parameter Weibull distribution and the loads carried by broken and intact fibers statisfy the global load sharing criterion. The composite can no longer support the applied load when the total loads supported by broken and intact fibers approach its maximum value. The conditions of a single matrix crack and matrix multicrackings for tensile strength considering oxidation time and temperature have been analyzed.

  20. 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.

  1. 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....

  2. Modeling of diffusion mechanism of conductive channel oxidation in a Pt/NiO/Pt memory switching structure

    Science.gov (United States)

    Sysun, V. I.; Bute, I. V.; Boriskov, P. P.

    2016-09-01

    The transition process from the low resistance state into the high resistance state in a Pt/NiO/Pt memory switching structure has been studied by numerical modeling. Detailed analysis shows, that thermally induced diffusion oxidation by nickel vacancies is the key factor for distortion of the channel metallic conductivity. Spatial dynamics of the process of oxidation defines channel narrowing mainly in its central part, and also sets the critical current through the structure sufficient for final rupture of the channel and the transition to high resistance state. The increase in critical current above the limit even by 10% reduces the switching time by an order of magnitude, which is in agreement with experiments. The developed radial diffusion model of conductive channel (or filaments) oxidation may be suitable for the analysis of switching effect a number of other ReRAM oxide structures.

  3. 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.

  4. Fuzzy-logic modeling of Fenton's strong chemical oxidation process treating three types of landfill leachates.

    Science.gov (United States)

    Sari, Hanife; Yetilmezsoy, Kaan; Ilhan, Fatih; Yazici, Senem; Kurt, Ugur; Apaydin, Omer

    2013-06-01

    Three multiple input and multiple output-type fuzzy-logic-based models were developed as an artificial intelligence-based approach to model a novel integrated process (UF-IER-EDBM-FO) consisted of ultrafiltration (UF), ion exchange resins (IER), electrodialysis with bipolar membrane (EDBM), and Fenton's oxidation (FO) units treating young, middle-aged, and stabilized landfill leachates. The FO unit was considered as the key process for implementation of the proposed modeling scheme. Four input components such as H(2)O(2)/chemical oxygen demand ratio, H(2)O(2)/Fe(2+) ratio, reaction pH, and reaction time were fuzzified in a Mamdani-type fuzzy inference system to predict the removal efficiencies of chemical oxygen demand, total organic carbon, color, and ammonia nitrogen. A total of 200 rules in the IF-THEN format were established within the framework of a graphical user interface for each fuzzy-logic model. The product (prod) and the center of gravity (centroid) methods were performed as the inference operator and defuzzification methods, respectively, for the proposed prognostic models. Fuzzy-logic predicted results were compared to the outputs of multiple regression models by means of various descriptive statistical indicators, and the proposed methodology was tested against the experimental data. The testing results clearly revealed that the proposed prognostic models showed a superior predictive performance with very high determination coefficients (R (2)) between 0.930 and 0.991. This study indicated a simple means of modeling and potential of a knowledge-based approach for capturing complicated inter-relationships in a highly non-linear problem. Clearly, it was shown that the proposed prognostic models provided a well-suited and cost-effective method to predict removal efficiencies of wastewater parameters prior to discharge to receiving streams.

  5. 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.

  6. The investigation of gadolinium oxide porous structure and refinement of the pore size distribution based on the NLDFT-models

    Science.gov (United States)

    Mashkovtsev, Maxim A.; Botalov, Maxim S.; Smyshlyaev, Denis V.; Kasimova, Renata E.; Bereskina, Polina A.; Vereshchagin, Artem O.

    2016-09-01

    The study focuses on the characterization of gadolinium oxide surface by the method of low-temperature adsorption/desorption of nitrogen. The specific surface area of gadolinium oxide, the average pore diameter and fractal dimensions were determined. The refinement of the pore distribution was performed on the basis of the NLDFT model. It was shown that there were three kinds of pores with average sizes of 150, 300 and 600 Å.

  7. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  8. Microstrain in nanostructured nickel oxide studied using isotropic and anisotropic models

    International Nuclear Information System (INIS)

    Nanostructured nickel oxide, NiO is synthesized through a novel chemical route using nickel chloride and ethanol amine as starting materials. The prepared samples are annealed at higher temperatures, viz. 350 °C, 400 °C, 500 °C and 600 °C. The samples are characterized using XRD, TEM, antioxidant activity and DC conductivity measurements. The crystallite size and microstrain in the samples are studied using Williamson-Hall (W-H) analysis assuming uniform deformation model, uniform deformation stress model and uniform deformation energy density model. The results obtained using three models yield microstrain values which decreases with increase of crystallite size. The average crystallite size and the microstrain of the samples measured from modified W-H plot using uniform energy density model are found to be most suitable. The study shows that the microstrain in nanostructured NiO originates due to the presence of Ni2+ and O2− vacancies and it is confirmed by the measurement of antioxidant activity and dc conductivity of the samples in vacuum and air ambience

  9. A novel parameter estimation method for metal oxide surge arrester models

    Indian Academy of Sciences (India)

    Mehdi Nafar; Gevork B Gharehpetian; Taher Niknam

    2011-12-01

    Accurate modelling and exact determination of Metal Oxide (MO) surge arrester parameters are very important for arrester allocation, insulation coordination studies and systems reliability calculations. In this paper, a new technique, which is the combination of Adaptive Particle Swarm Optimization (APSO) and Ant Colony Optimization (ACO) algorithms and linking the MATLAB and EMTP, is proposed to estimate the parameters of MO surge arrester models. The proposed algorithm is named Modified Adaptive Particle Swarm Optimization (MAPSO). In the proposed algorithm, to overcome the drawback of the PSO algorithm (convergence to local optima), the inertia weight is tuned by using fuzzy rules and the cognitive and the social parameters are self-adaptively adjusted. Also, to improve the global search capability and prevent the convergence to local minima, ACO algorithm is combined to the proposed APSO algorithm. The transient models of MO surge arrester have been simulated by using ATP-EMTP. The results of simulations have been applied to the program, which is based on MAPSO algorithm and can determine the fitness and parameters of different models. The validity and the accuracy of estimated parameters of surge arrester models are assessed by comparing the predicted residual voltage with experimental results.

  10. Modeling a reversible solid oxide fuel cell as a storage device within AC power networks

    Energy Technology Data Exchange (ETDEWEB)

    Ren, J.; Roscoe, A.J.; Burt, G. [Department of Electronic and Electrical Engineering, Royal College, University of Strathclyde, Glasgow (United Kingdom); Gamble, S.R.; Irvine, J.T.S. [School of Chemistry, University of St. Andrews, Purdie Building, St. Andrews (United Kingdom)

    2012-10-15

    A reversible solid oxide fuel cell (RSOFC) system, consisting of a RSOFC stack, heat store, and electrical inverters to convert DC to AC power, is shown by computer modeling to have the potential to efficiently store electrical energy. This paper describes the modeling of a single RSOFC, based on a proposed cell geometry, empirical data on the resistivities of the components, and calculation of activation and diffusion polarization resistances from electrochemical theory. Data from ac impedance spectroscopy measurements on symmetrical cells are used to model RSOFC impedance. A RSOFC stack is modeled by electrically linking the individual cells inside a pressurized vessel. A phase change heat store is added to improve energy storage efficiency. The model is implemented in MATLAB {sup registered} /Simulink {sup registered}. Two competing inverter control schemes are compared, trading off DC bus ripple against AC power quality. It is found that selection of appropriate DC bus capacitance is important in certain scenarios, with potential system cost implications. It is shown that the system can store electrical energy at an efficiency of 64% over a single discharge-charge cycle, i.e., hydrogen to electricity and heat to hydrogen. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. 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.

  12. 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)

  13. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells. PMID:27137703

  14. Modeling mass transfer in solid oxide fuel cell anode: II. H2/CO co-oxidation and surface diffusion in synthesis-gas operation

    Science.gov (United States)

    Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

    2016-08-01

    Following the previous work on comparing performance of Fickian, Stefan-Maxwell and dusty-gas model for mass transfer in single fuel system, this article is focused on the electrochemistry and transport in the anode of solid oxide fuel cell using H2sbnd H2Osbnd COsbnd CO2sbnd N2 hybrid fuel. Under the standard framework of the dusty-gas model combined with the Butler-Volmer equation, it carries out a macroscopic area-specific modeling work. More specifically, two variables of hydrogen current fraction and enhancement factor are well defined and solved for the electrochemical co-oxidation of H2 and CO, and the diffusion equivalent circuit model is introduced to describe more comprehensively the resistance of mass transfer including molecular/Knudsen diffusion and surface diffusion. The model has been validated well in full region of Vsbnd I performance of an experimental anode-supported button cell. An approximate analytical solution of the hydrogen current fraction is also presented for explicit computation. Comparison between the results by different approaches for the effective diffusivity shows the importance of right mass-transfer modeling.

  15. 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...

  16. Modelling a Combined Heat and Power Plant based on Gasification, Micro Gas Turbine and Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Bang-Møller, Christian; Rokni, Masoud

    2009-01-01

    A system level modelling study on two combined heat and power (CHP) systems both based on biomass gasification. One system converts the product gas in a micro gas turbine (MGT) and the other in a combined solid oxide fuel cell (SOFC) and MGT arrangement. An electrochemical model of the SOFC has...

  17. Kinetic Monte Carlo Simulation of the oscillatory catalytic CO oxidation using a modified Ziff-Gulari-Barshad model

    Science.gov (United States)

    Sinha, Indrajit; Mukherjee, Ashim K.

    2014-03-01

    The oxidation of CO on Pt-group metal surfaces has attracted widespread attention since a long time due to its interesting oscillatory kinetics and spatiotemporal behavior. The use of STM in conjunction with other experimental data has confirmed the validity of the surface reconstruction (SR) model under low pressure and the more recent surface oxide (SO) model which is possible under sub-atmospheric pressure conditions [1]. In the SR model the surface is periodically reconstructed below a certain low critical CO-coverage and this reconstruction is lifted above a second, higher critical CO-coverage. Alternatively the SO model proposes periodic switching between a low-reactivity metallic surface and a high-reactivity oxide surface. Here we present an overview of our recent kinetic Monte Carlo (KMC) simulation studies on the oscillatory kinetics of surface catalyzed CO oxidation. Different modifications of the lattice gas Ziff-Gulari-Barshad (ZGB) model have been utilized or proposed for this purpose. First we present the effect of desorption on the ZGB reactive to poisoned irreversible phase transition in the SR model. Next we discuss our recent research on KMC simulation of the SO model. The ZGB framework is utilized to propose a new model incorporating not only the standard Langmuir-Hinshelwood (LH) mechanism, but also introducing the Mars-van Krevelen (MvK) mechanism for the surface oxide phase [5]. Phase diagrams, which are plots between long time averages of various oscillating quantities against the normalized CO pressure, show two or three transitions depending on the CO coverage critical threshold (CT) value beyond which all adsorbed oxygen atoms are converted to surface oxide.

  18. Model testing for nitrous oxide (N2O) fluxes from Amazonian cattle pastures

    Science.gov (United States)

    Meurer, Katharina H. E.; Franko, Uwe; Spott, Oliver; Stange, C. Florian; Jungkunst, Hermann F.

    2016-10-01

    Process-oriented models have become important tools in terms of quantification of environmental changes, for filling measurement gaps, and building of future scenarios. It is especially important to couple model application directly with measurements for remote areas, such as Southern Amazonia, where direct measurements are difficult to perform continuously throughout the year. Processes and resulting matter fluxes may show combinations of steady and sudden reactions to external changes. The potent greenhouse gas nitrous oxide (N2O) is known for its sensitivity to e.g. precipitation events, resulting in intense but short-term peak events (hot moments). These peaks have to be captured for sound balancing. However, prediction of the effect of rainfall events on N2O peaks is not trivial, even for areas under distinct wet and dry seasons. In this study, we used process-oriented models in both a pre-and post-measurement manner in order to (a) determine important periods for N2O-N emissions under Amazonian conditions and (b) calibrate the models to Brazilian pastures based on measured data of environment conditions (soil moisture and Corg) and measured N2O-N fluxes. During the measurement period (early wet season), observed emissions from three cattle pastures did not react to precipitation events, as proposed by the models. Here both process understanding and models have to be improved by long-term data in high resolution in order to prove or disprove a lacking of N2O-N peaks. We strongly recommend the application of models as planning tools for field campaigns, but we still suggest model combinations and simultaneous usage.

  19. 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

    Directory of Open Access Journals (Sweden)

    S. H. Jathar

    2015-09-01

    Full Text Available 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 UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are 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 tested. Consequently, the use of low and high NOx yields

  20. Polyhydroxylated fullerene nanoparticles attenuate brain infarction and oxidative stress in rat model of ischemic stroke

    Science.gov (United States)

    Vani, Javad Rasouli; Mohammadi, Mohammad Taghi; Foroshani, Mahsa Sarami; Jafari, Mahvash

    2016-01-01

    Oxidative stress is the common underlying mechanism of damage in ischemic stroke. Therefore, we aimed to evaluate the possible protective effects of polyhydroxylated fullerene derivatives on brain infarction and oxidative/nitrosative stress in a rat model of ischemic stroke. The experiment was performed by four groups of rats (each; n=12); Sham, Control ischemia, and ischemic treatment groups (Pretreatment and Posttreatment). Brain ischemia was induced by 90 min middle cerebral artery occlusion (MCAO) followed by 24 hours reperfusion. Rats received fullerene nanoparticles at dose of 1 mg/kg 30 min before MCAO and immediately after beginning of reperfusion. Infarct volume, contents of malondialdehyde (MDA), glutathione (GSH) and nitrate as well as superoxide dismutase (SOD) activity were assessed 24 hours after termination of MCAO. Brain infarct volume was 310 ± 21 mm3 in control group. Administration of fullerene nanoparticles before and after MCAO significantly decreased the infarct volume by 53 % (145 ± 45 mm3) and 81 % (59 ± 13 mm3), respectively. Ischemia also enhanced MDA and nitrate contents of ischemic hemispheres by 45 % and 25 % , respectively. Fullerene nanoparticles considerably reduced the MDA and nitrate contents of ischemic hemispheres before MCAO by 58 % and 17 % , respectively, and after MCAO by 38 % and 21 % , respectively. Induction of MCAO significantly decreased GSH content (19 % ) and SOD activity (52 % ) of ischemic hemispheres, whereas fullerene nanoparticles increased the GSH content and SOD activity of ischemic hemispheres by 19 % and 52 % before MCAO, respectively, and 21 % and 55 % after MCAO, respectively. Our findings indicate that fullerene nanoparticles, as a potent scavenger of free radicals, protect the brain cells against ischemia/reperfusion injury and inhibit brain oxidative/nitrosative damage.

  1. Carnosine and taurine treatments diminished brain oxidative stress and apoptosis in D-galactose aging model.

    Science.gov (United States)

    Aydın, A Fatih; Çoban, Jale; Doğan-Ekici, Işın; Betül-Kalaz, Esra; Doğru-Abbasoğlu, Semra; Uysal, Müjdat

    2016-04-01

    D-galactose (GAL) has been used as an animal model for brain aging and antiaging studies. GAL stimulates oxidative stress in several tissues including brain. Carnosine (CAR; β-alanil-L-histidine) and taurine (TAU; 2-aminoethanesulfonic acid) exhibit antioxidant properties. CAR and TAU have anti-aging and neuroprotective effects. We investigated the effect of CAR and TAU supplementations on oxidative stress and brain damage in GAL-treated rats. Rats received GAL (300 mg/kg; s.c.; 5 days per week) alone or together with CAR (250 mg/kg/daily; i.p.; 5 days per week) or TAU (2.5% w/w; in rat chow) for 2 months. Brain malondialdehyde (MDA), protein carbonyl (PC) and glutathione (GSH) levels and superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), glutathione transferase (GST) and acetylcholinesterase (AChE) activities were determined. Expressions of B cell lymphoma-2 (Bcl-2), Bax and caspase-3 were also evaluated in the brains by immunohistochemistry. GAL treatment increased brain MDA and PC levels and AChE activities. It decreased significantly brain GSH levels, SOD and GSH-Px but not GST activities. GAL treatment caused histopathological changes and increased apoptosis. CAR and TAU significantly reduced brain AChE activities, MDA and PC levels and elevated GSH levels in GAL-treated rats. CAR, but not TAU, significantly increased low activities of SOD and GSH-Px. Both CAR and TAU diminished apoptosis and ameliorated histopathological findings in the brain of GAL-treated rats. Our results indicate that CAR and TAU may be effective to prevent the development of oxidative stress, apoptosis and histopathological deterioration in the brain of GAL-treated rats. PMID:26518192

  2. alpha-Synuclein budding yeast model: toxicity enhanced by impaired proteasome and oxidative stress.

    Science.gov (United States)

    Sharma, Nijee; Brandis, Katrina A; Herrera, Sara K; Johnson, Brandon E; Vaidya, Tulaza; Shrestha, Ruja; Debburman, Shubhik K

    2006-01-01

    Parkinson's disease (PD) is a common neurodegenerative disorder that results from the selective loss of midbrain dopaminergic neurons. Misfolding and aggregation of the protein alpha-synuclein, oxidative damage, and proteasomal impairment are all hypotheses for the molecular cause of this selective neurotoxicity. Here, we describe a Saccharomyces cerevisiae model to evaluate the misfolding, aggregation, and toxicity-inducing ability of wild-type alpha-synuclein and three mutants (A30P, A53T, and A30P/A53T), and we compare regulation of these properties by dysfunctional proteasomes and by oxidative stress. We found prominent localization of wild-type and A53T alpha-synuclein near the plasma membrane, supporting known in vitro lipid-binding ability. In contrast, A30P was mostly cytoplasmic, whereas A30P/A53T displayed both types of fluorescence. Surprisingly, alpha-synuclein was not toxic to several yeast strains tested. When yeast mutants for the proteasomal barrel (doa3-1) were evaluated, delayed alpha-synuclein synthesis and membrane association were observed; yeast mutant for the proteasomal cap (sen3-1) exhibited increased accumulation and aggregation of alpha-synuclein. Both sen3-1and doa3-1 mutants exhibited synthetic lethality with alpha-synuclein. When yeasts were challenged with an oxidant (hydrogen peroxide), alpha-synuclein was extremely lethal to cells that lacked manganese superoxide dismutase Mn-SOD (sod2Delta) but not to cells that lacked copper, zinc superoxide dismutase Cu,Zn-SOD (sod1Delta). Despite the toxicity, sod2Delta cells never displayed intracellular aggregates of alpha-synuclein. We suggest that the toxic alpha-synuclein species in yeast are smaller than the visible aggregates, and toxicity might involve alpha-synuclein membrane association. Thus, yeasts have emerged effective organisms for characterizing factors and mechanisms that regulate alpha-synuclein toxicity.

  3. Influence of agricultural management on nitrous oxide emissions: comparison of different modelling approaches

    Science.gov (United States)

    Klier, C.; Gayler, S.; Haberbosch, C.; Ruser, R.; Stenger, R.; Flessa, H.; Priessack, E.

    2010-05-01

    Intensive agricultural land use is considered to be the major source of the anthropogenic contribution to the increase in atmospheric nitrous oxide (N2O) concentration during the last decades. Mathematical models help to understand interacting processes in the nitrogen cycle and state variables affecting N2O emissions. Most of the simulation models which have been used to estimate N2O emissions from soils under field conditions represent the underlying processes of denitrification or nitrification by first order rates without modelling the gaseous N2O transport process. In the first part of the study we compare two modelling approaches of the modular nitrogen modelling system Expert-N for their ability to describe and quantify the seasonal variations of N2O fluxes in a potato-cropped soil. Model 1 assumes a fixed N2O:N2 ratio for N2O production and neglects the transport of N2O in the soil profile, Model 2 explicitly considers a N2O transport and assumes a dynamic reduction of N2O to N2. Data for model evaluation arise from an experiment, where N2O fluxes were monitored over the vegetation period, using a closed chamber technique. Experimental results showed a variation of N and O2 supplies between the ridge soil and inter-row soil of the potato plantation and a corresponding impact on N2O release to atmosphere. Thus, in the second part of the study we applied a multiregion modelling approach to get a spatially explicit modelling tool. In the multiregion approach a heterogeneous soil hydraulic regime is subdivided into finite, multiple, hydraulically interacting regions in the form of soil columns. Modelling results showed for the first part of the study that both modelling approaches were able to describe the observed seasonal dynamics of N2O emissions and events of high N2O emissions due to increased denitrification activity after heavy precipitation and fertiliser application. Extremely high emission rates from the inter-row soil of the potato plantation were

  4. Process flow model of solid oxide fuel cell system supplied with sewage biogas

    Science.gov (United States)

    Van herle, J.; Maréchal, F.; Leuenberger, S.; Membrez, Y.; Bucheli, O.; Favrat, D.

    A model for a 100 kW class solid oxide fuel cell (SOFC) system running on biogas from a sewage sludge digestion plant was implemented in a process flow scheme using external steam reforming. The model stack consisted of planar anode supported cells operated at 800 °C displaying state-of-the-art electrochemical performance (0.15 W/cm 2 at 80% fuel utilisation). Real annual data from an existing sewage plant were used as input to the model. From the input of 43 m 3/h biogas (63% CH 4), equivalent to 269 kW (higher heating value, HHV), the SOFC stack was calculated to deliver 131 kW el electricity (48.7%) using a steam-to-carbon ratio of 0.5. This would allow the sewage site to more than cover its own electrical needs, hence to depollute the waste stream at negative energy cost. In its current exploitation using a low efficient gas engine (130 kW), the site is only ≈50% self-sufficient. Special attention was given to the thermal balance of the stack. The stack developed heat (143 kW) could be balanced by endothermal reforming (78 kW) and by cathode excess air λ (=3), allowing a temperature difference between stack inlet and outlet of 200 K. The case was compared to other fuel scenarios. Steam-added biogas behaves basically identically to steam-reformed methane. For partial oxidation of biogas or pure hydrogen feeding, electrical efficiency drops to under 43% while λ needs to be raised to 4.5 to maintain the 200 K thermal gradient over the stack.

  5. 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%.

  6. Model uncertainties affecting satellite-based inverse modeling of nitrogen oxides emissions and implications for surface ozone simulation

    Directory of Open Access Journals (Sweden)

    J.-T. Lin

    2012-06-01

    Full Text Available Errors in chemical transport models (CTMs interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2 and emissions of nitrogen oxides (NOx have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 22% in July and 10% in January. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitudes if the model is used

  7. Paricalcitol may improve oxidative DNA damage on experimental amikacin-induced nephrotoxicity model.

    Science.gov (United States)

    Bulut, Gulay; Basbugan, Yildiray; Ari, Elif; Erten, Remzi; Bektas, Havva; Alp, Hamit Hakan; Bayram, Irfan

    2016-06-01

    This study aimed to investigate the possible protective effect of paricalcitol on experimental amikacin-induced nephrotoxicity model in rats. Wistar albino rats (n = 32) were allocated into four equal groups of eight each, the control (Group C), paricalcitol (Group P), amikacin-induced nephrotoxicity (Group A), and paricalcitol-treated amikacin-induced nephrotoxicity (Group A + P) groups. Paricalcitol was given intra-peritoneally at a dose of 0.4 μg/kg/d for 5 consecutive days prior to induction of amikacin-induced nephrotoxicity. Intra-peritoneal amikacin (1.2 g/kg) was used to induce nephrotoxicity at day 4. Renal function parameters, oxidative stress biomarkers, oxidative DNA damage (8-hydroxy-2'-deoxyguanosine/deoxyguanosine ratio), kidney histology, and vascular endothelial growth factor (VEGF) immunoexpression were determined. Group A + P had lower mean fractional sodium excretion (p < 0.001) as well as higher creatinine clearance (p = 0.026) than the amikacin group (Group A). Renal tissue malondialdehyde levels (p = 0.035) and serum 8-hydroxy-2'-deoxyguanosine/deoxyguanosine ratio (8-OHdG/dG ratio) (p < 0.001) were significantly lower; superoxide dismutase (p = 0.024) and glutathione peroxidase (p = 0.007) activities of renal tissue were significantly higher in group A + P than in group A. The mean scores of tubular necrosis (p = 0.024), proteinaceous casts (p = 0.038), medullary congestion (p = 0.035), and VEGF immunoexpression (p = 0.018) were also lower in group A + P when compared with group A. This study demonstrates the protective effect of paricalcitol in the prevention of amikacin-induced nephrotoxicity in an experimental model. Furthermore, it is the first study to demonstrate that paricalcitol improves oxidative DNA damage in an experimental acute kidney injury model.

  8. Detailed dynamic Solid Oxide Fuel Cell modeling for electrochemical impedance spectra simulation

    Science.gov (United States)

    Hofmann, Ph.; Panopoulos, K. D.

    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™. 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.

  9. 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)

  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. 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. PMID:7574883

  12. One-step synthesis of iron oxide polypyrrole nanoparticles encapsulating ketoprofen as model of hydrophobic drug.

    Science.gov (United States)

    Attia, Mohamed F; Anton, Nicolas; Khan, Ikram Ullah; Serra, Christophe A; Messaddeq, Nadia; Jakhmola, Anshuman; Vecchione, Raffaele; Vandamme, Thierry

    2016-07-11

    This study reports a novel one-step synthesis of hybrid iron oxide/polypyrrole multifunctional nanoparticles encapsulating hydrophobic drug and decorated with polyethylene glycol. The overall process is based on the in situ chemical oxidative polymerization of pyrrole along with the reduction of ferric chloride (FeCl3) in the presence of ketoprofen as model drug and PEGylated surfactants. The final product is a nanocomposite composed of polypyrrole and a mixture of FeO/Fe2O3. Different concentrations of ketoprofen were encapsulated in the nanocomposite, and were characterized by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Encapsulation efficiency of the final product was measured by absorption, which can reach up to 98%. The release experiments confirmed complete drug release after about 3h in PBS solution. Morphological characterization of the nanocomposites was performed by electron microscopy (scanning and transmission electron microscopy) which confirmed the spherical geometry and opaque nature of nanoparticles with average particle size well below 50 nm. The final product is multifunctional system, which could act both as a nanocarrier for drug molecules as well as a contrasting agent. Magnetic relaxometry studies confirmed their possible applications as potential contrast agent in the field of magnetic resonance imaging (MRI). PMID:27163525

  13. A model for the description of oxidation in sulfidic waste rock dumps

    International Nuclear Information System (INIS)

    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

  14. A Summary of the NASA Lightning Nitrogen Oxides Model (LNOM) and Recent Results

    Science.gov (United States)

    Koshak, William; Peterson, Harld

    2011-01-01

    The NASA Marshall Space Flight Center introduced the Lightning Nitrogen Oxides Model (LNOM) a couple of years ago to combine routine state-of-the-art measurements of lightning with empirical laboratory results of lightning NOx production. The routine measurements included VHF lightning source data [such as from the North Alabama Lightning Mapping Array (LMA)], and ground flash location, peak current, and stroke multiplicity data from the National Lightning Detection Network(TradeMark) (NLDN). Following these initial runs of LNOM, the model was updated to include several non-return stroke lightning NOx production mechanisms, and provided the impact of lightning NOx on an August 2006 run of CMAQ. In this study, we review the evolution of the LNOM in greater detail and discuss the model?s latest upgrades and applications. Whereas previous applications were limited to five summer months of data for North Alabama thunderstorms, the most recent LNOM analyses cover several years. The latest statistics of ground and cloud flash NOx production are provided.

  15. Prediction model for oxide thickness on aluminum alloy cladding during irradiation

    International Nuclear Information System (INIS)

    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)

  16. 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

  17. Impact of oxide thickness on gate capacitance – Modelling and comparative analysis of GaN-based MOSHEMTs

    Indian Academy of Sciences (India)

    Kanjalochan Jena; Raghunandan Swain; T R Lenka

    2015-12-01

    In this paper, we have developed a mathematical model to predict the behaviour of gate capacitance and threshold voltage with nanoscale variation of oxide thickness in AlInN/GaN and AlGaN/GaN metal oxide semiconductor high electron mobility transistor (MOSHEMT). The results obtained from the model are compared with the TCAD simulation results to validate the model. It is observed that AlInN/GaN MOSHEMT has an advantage of significant decrease in gate capacitance up to 0.0079 pF/m2 with increase in oxide thickness up to 5 nm as compared to conventional AlGaN/GaN MOSHEMT. This decrease in gate capacitance in AlInN/GaN MOSHEMT reduces the propagation delay and hence improves the RF performance of the device.

  18. Modeling uncertainties for tropospheric nitrogen dioxide columns affecting satellite-based inverse modeling of nitrogen oxides emissions

    Directory of Open Access Journals (Sweden)

    J.-T. Lin

    2012-12-01

    Full Text Available Errors in chemical transport models (CTMs interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2 and emissions of nitrogen oxides (NOx have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 18% in July and 8% in January, the most important factor being modified uptake of the hydroperoxyl radical (HO2 on aerosols. This suggests a possible systematic model

  19. Mutual sensitization of the oxidation of nitric oxide and a natural gas blend in a JSR at elevated pressure: experimental and detailed kinetic modeling study.

    Science.gov (United States)

    Dagaut, Philippe; Dayma, Guillaume

    2006-06-01

    The mutual sensitization of the oxidation of NO and a natural gas blend (methane-ethane 10:1) was studied experimentally in a fused silica jet-stirred reactor operating at 10 atm, over the temperature range 800-1160 K, from fuel-lean to fuel-rich conditions. Sonic quartz probe sampling followed by on-line FTIR analyses and off-line GC-TCD/FID analyses were used to measure the concentration profiles of the reactants, the stable intermediates, and the final products. A detailed chemical kinetic modeling of the present experiments was performed yielding an overall good agreement between the present data and this modeling. According to the proposed kinetic scheme, the mutual sensitization of the oxidation of this natural gas blend and NO proceeds through the NO to NO2 conversion by HO2, CH3O2, and C2H5O2. The detailed kinetic modeling showed that the conversion of NO to NO2 by CH3O2 and C2H5O2 is more important at low temperatures (ca. 820 K) than at higher temperatures where the reaction of NO with HO2 controls the NO to NO2 conversion. The production of OH resulting from the oxidation of NO by HO2, and the production of alkoxy radicals via RO2 + NO reactions promotes the oxidation of the fuel. A simplified reaction scheme was delineated: NO + HO2 --> NO2 + OH followed by OH + CH4 --> CH3 + H2O and OH + C2H6 --> C2H5 + H2O. At low-temperature, the reaction also proceeds via CH3 + O2 (+ M) --> CH3O2 (+ M); CH3O2 + NO --> CH3O + NO2 and C2H5 + O2 --> C2H5O2; C2H5O2 + NO --> C2H5O + NO2. At higher temperature, methoxy radicals are produced via the following mechanism: CH3 + NO2 --> CH3O + NO. The further reactions CH3O --> CH2O + H; CH2O + OH --> HCO + H2O; HCO + O2 --> HO2 + CO; and H + O2 + M --> HO2 + M complete the sequence. The proposed model indicates that the well-recognized difference of reactivity between methane and a natural gas blend is significantly reduced by addition of NO. The kinetic analyses indicate that in the NO-seeded conditions, the main production

  20. Modeling the effects of vegetation on methane oxidation and emissions through soil landfill final covers across different climates.

    Science.gov (United States)

    Abichou, Tarek; Kormi, Tarek; Yuan, Lei; Johnson, Terry; Francisco, Escobar

    2015-02-01

    Plant roots are reported to enhance the aeration of soil by creating secondary macropores which improve the diffusion of oxygen into soil as well as the supply of methane to bacteria. Therefore, methane oxidation can be improved considerably by the soil structuring processes of vegetation, along with the increase of organic biomass in the soil associated with plant roots. This study consisted of using a numerical model that combines flow of water and heat with gas transport and oxidation in soils, to simulate methane emission and oxidation through simulated vegetated and non-vegetated landfill covers under different climatic conditions. Different simulations were performed using different methane loading flux (5-200 g m(-2) d(-1)) as the bottom boundary. The lowest modeled surface emissions were always obtained with vegetated soil covers for all simulated climates. The largest differences in simulated surface emissions between the vegetated and non-vegetated scenarios occur during the growing season. Higher average yearly percent oxidation was obtained in simulations with vegetated soil covers as compared to non-vegetated scenario. The modeled effects of vegetation on methane surface emissions and percent oxidation were attributed to two separate mechanisms: (1) increase in methane oxidation associated with the change of the physical properties of the upper vegetative layer and (2) increase in organic matter associated with vegetated soil layers. Finally, correlations between percent oxidation and methane loading into simulated vegetated and non-vegetated covers were proposed to allow decision makers to compare vegetated versus non-vegetated soil landfill covers. These results were obtained using a modeling study with several simplifying assumptions that do not capture the complexities of vegetated soils under field conditions.

  1. Performance Model for High-Power Lithium Titanate Oxide Batteries based on Extended Characterization Tests

    DEFF Research Database (Denmark)

    Stroe, Ana-Irina; Swierczynski, Maciej Jozef; Stroe, Daniel Ioan;

    2015-01-01

    Lithium-ion (Li-ion) batteries are found nowadays not only in portable/consumer electronics but also in more power demanding applications, such as stationary renewable energy storage, automotive and back-up power supply, because of their superior characteristics in comparison to other energy...... storage technologies. Nevertheless, prior to be used in any of the aforementioned application, a Li-ion battery cell must be intensively characterized and its behavior needs to be understood. This can be realized by performing extended laboratory characterization tests and developing Li-ion battery...... model for a commercially available 13Ah high-power lithium titanate oxide battery cell based on laboratory-performed extended characterization tests....

  2. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rau, M.S.; Gennero de Chialvo, M.R. [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina); Chialvo, A.C., E-mail: achialvo@fiq.unl.edu.a [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina)

    2010-07-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H{sub 2}SO{sub 4} solution at different rotation rates ({omega}). 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 {omega}{sup 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.

  3. Alzheimer's Proteins, Oxidative Stress, and Mitochondrial Dysfunction Interplay in a Neuronal Model of Alzheimer's Disease

    Science.gov (United States)

    Bobba, Antonella; Petragallo, Vito A.; Marra, Ersilia; Atlante, Anna

    2010-01-01

    In this paper, we discuss the interplay between beta-amyloid (Aβ) 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. PMID:20862336

  4. Phase diagram of the Cu-O model in the oxide superconductors: Variational Monte Carlo study

    Science.gov (United States)

    Yanagisawa, Takashi; Koike, Soh; Yamaji, Kunihiko

    2000-07-01

    A variational Monte Carlo method is formulated to study the ground state of the model for the Cu-O plane in the oxide superconductors. The possibility of superconductivity is investigated employing the Gutzwiller-projected BCS and SDW wave functions with respect to dependences on electron density ρ and transfer tpp between neighboring oxygen orbitals. Near half-filling the SDW state is most stable for both the hole and electron doping cases. Away from half-filling when hole doping ratio δ∼0.2, the d-wave superconducting state turns out to be more favorable than the SDW state. The superconducting condensation energy is in reasonable agreement with the experimental value obtained from the critical magnetic field Hc.

  5. Importance of pressure gradient in solid oxide fuel cell electrodes for modeling study

    Science.gov (United States)

    Ni, Meng; Leung, Dennis Y. C.; Leung, Michael K. H.

    The pressure gradients in the electrodes of a solid oxide fuel cell (SOFC) are frequently neglected without any justification in calculating the concentration overpotentials of the SOFC electrodes in modeling studies. In this short communication, a comparative study has been conducted to study the effect of pressure gradients on mass transfer and the resulting concentration overpotentials of an SOFC running on methane (CH 4) fuel. It is found that the pressure gradients in both anode and cathode are significant in the fuel cell electrochemical activities. Neglecting the anode pressure gradient in the calculation can lead to underestimation of the concentration overpotential by about 20% at a typical current density of 5000 A m -2 and at a temperature of 1073 K. The deviation can be even larger at a higher temperature. At the cathode, neglecting the pressure gradient can result in overestimation of the concentration overpotential by about 10% under typical working conditions.

  6. An atomic charge model for graphene oxide for exploring its bioadhesive properties in explicit water

    Energy Technology Data Exchange (ETDEWEB)

    Stauffer, D.; Dragneva, N.; Floriano, W. B.; Rubel, O. [Thunder Bay Regional Research Institute, 290 Munro St, Thunder Bay, Ontario P7B 6V4 (Canada); Lakehead University, 955 Oliver Road, Thunder Bay, Ontario P7A 7T1 (Canada); Mawhinney, R. C. [Lakehead University, 955 Oliver Road, Thunder Bay, Ontario P7A 7T1 (Canada); Fanchini, G. [Physics and Astronomy, University of Western Ontario, 1151 Richmond St, London, Ontario N6A 3K7 (Canada); French, S. [University of Calgary, South Health Campus, 4448 Front St. SE, Calgary, Alberta T3M 1M4 (Canada)

    2014-07-28

    Graphene Oxide (GO) has been shown to exhibit properties that are useful in applications such as biomedical imaging, biological sensors, and drug delivery. The binding properties of biomolecules at the surface of GO can provide insight into the potential biocompatibility of GO. Here we assess the intrinsic affinity of amino acids to GO by simulating their adsorption onto a GO surface. The simulation is done using Amber03 force-field molecular dynamics in explicit water. The emphasis is placed on developing an atomic charge model for GO. The adsorption energies are computed using atomic charges obtained from an ab initio electrostatic potential based method. The charges reported here are suitable for simulating peptide adsorption to GO.

  7. 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.

  8. Deterioration of yttria-stabilized zirconia by boron carbide alone or mixed with metallic or oxidized Fe, Cr, Zr mixtures

    Science.gov (United States)

    De Bremaecker, A.; Ayrault, L.; Clément, B.

    2014-08-01

    In the frame of severe accident conditions (PHEBUS FPT3 test), different experiments were carried out on the interactions of 20% yttria-stabilized zirconia (YSZ) and 20% ceria-stab zirconia with boron carbide or its oxidation products (B2O3): either tests under steam between 1230° and 1700 °C with B4C alone or B4C mixed with metals, either tests under Ar with boron oxide present in a mixture of iron and chromium oxides. In all cases an interaction was observed with formation of intergranular yttrium borate. At 1700 °C boron oxide is able to “pump out” the Y stabiliser from the YSZ grains but also some trace elements (Ca and Al) and to form a eutectic containing YBO3 and yttrium calcium oxy-borate (YCOB). At the same time a substantial swelling (“bloating”) of the zirconia happens, qualitatively similar to the foaming of irradiated fuel in contact with a Zr-melt. In all samples the lowering of the Y (or Ce)-content in the YSZ grains is so sharp that in the interaction layers zirconia is no longer stabilized. This is important when YSZ is envisaged as simulant of UO2 or as inert matrix for Am-transmutation.

  9. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2009-04-01

    Full Text Available We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1 and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM. Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(OOONO2. Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2, methyl peroxide (CH3OOH, methanol (CH3OH, formaldehyde (HCHO, peroxy acetyl nitrate (PAN, and formic and acetic acids (HCOOH and CH3C(OOH, being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK, methacrolein (MACR, hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO, propene (CH2=CHCH3 and glyoxal (CHOCHO with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by

  10. Behavioral despair associated with a mouse model of Crohn's disease: Role of nitric oxide pathway.

    Science.gov (United States)

    Heydarpour, Pouria; Rahimian, Reza; Fakhfouri, Gohar; Khoshkish, Shayan; Fakhraei, Nahid; Salehi-Sadaghiani, Mohammad; Wang, Hongxing; Abbasi, Ata; Dehpour, Ahmad Reza; Ghia, Jean-Eric

    2016-01-01

    Crohn's disease (CD) is associated with increased psychiatric co-morbidities. Nitric oxide (NO) is implicated in inflammation and tissue injury in CD, and it may also play a central role in pathogenesis of the accompanying behavioral despair. This study investigated the role of the NO pathway in behavioral despair associated with a mouse model of CD. Colitis was induced by intrarectal (i.r.) injection of 2,4,6-trinitrobenzenesulfonic acid (10mg TNBS in 50% ethanol). Forced swimming test (FST), pharmacological studies and tissues collection were performed 72 h following TNBS administration. To address a possible inflammatory origin for the behavioral despair following colitis induction, tumor necrosis factor-alpha (TNF-α) level was measured in both the hippocampal and colonic tissue samples. In parallel, hippocampal inducible nitric oxide synthase (iNOS) and nitrite level were evaluated. Pharmacological studies targeting the NO pathway were performed 30-60 min before behavioral test. Colitis was confirmed by increased colonic TNF-α level and microscopic score. Colitic mice demonstrated a significantly higher immobility time in the FST associated to a significant increase of hippocampal TNF-α, iNOS expression and nitrite content. Acute NOS inhibition using either Nω-nitro-l-arginine methyl ester (a non-specific NOS inhibitor) or aminoguanidine hydrochloride (a specific iNOS inhibitor) decreased the immobility time in colitic groups. Moreover, acute treatment with both NOS inhibitors decreased the TNF-α level and nitrite content in the hippocampal samples. This study suggests that the NO pathway may be involved in the behavioral effects in the mouse TNBS model of CD. These findings endow new insights into the gut-brain communication during the development of colonic inflammation, which may ultimately lead to improved therapeutic strategies to combat behavior changes associated with gastrointestinal disorders.

  11. The Effect of Learning Cycle Model on Preservice Chemistry Teachers’ Understanding of Oxidation Reduction Topic and Thinking Skills

    Directory of Open Access Journals (Sweden)

    Senar Temel

    2012-06-01

    Full Text Available In the study, it was aimed to examine preservice chemistry teachers’ understanding level of oxidation and reduction topic before and after the learning cycle model application and to determine the effect of this model on their understanding level of this topic and lower and higher order thinking skills. In the study, it was aimed to examine preservice chemistry teachers’ understanding level of oxidation and reduction topic before and after the learning cycle model application and to determine the effect of this model on their understanding level of this topic and lower and higher order thinking skills. Thirty preservice chemistry teachers from Hacettepe University, Faculty of Education, Department of Chemistry Education participated in the study. Data were obtained by Oxidation Reduction Achievement Test which is consisted of twelve open ended questions prepared according to Bloom Taxonomy. At the end of the study, it was determined that preservice chemistry teachers’ understanding level of oxidation reduction topic is low before the learning cycle model application but a significant increase in their understanding level of this topic was determined after the application. It was concluded that the learning cycle model provides a significant increase in their higher and lower order thinking skills via paired sample t-tests.

  12. Differential Fmo3 gene expression in various liver injury models involving hepatic oxidative stress in mice

    International Nuclear Information System (INIS)

    Flavin-containing monooxygenase-3 (FMO3) catalyzes metabolic reactions similar to cytochrome P450 monooxygenase, however, most metabolites of FMO3 are considered non-toxic. Recent findings in our laboratory demonstrated Fmo3 gene induction following toxic acetaminophen (APAP) treatment in mice. The goal of this study was to evaluate Fmo3 gene expression in other diverse mouse models of hepatic oxidative stress and injury. Fmo3 gene regulation by Nrf2 was also investigated using Nrf2 knockout (Nrf2 KO) mice. In our studies, male C57BL/6J mice were treated with toxic doses of hepatotoxicants or underwent bile duct ligation (BDL, 10 days). Hepatotoxicants included APAP (400 mg/kg, 24–72 h), alpha-naphthyl isothiocyanate (ANIT; 50 mg/kg, 2–48 h), carbon tetrachloride (CCl4; 10 or 30 μL/kg, 24 and 48 h) and allyl alcohol (AlOH; 30 or 60 mg/kg, 6 and 24 h). Because oxidative stress activates nuclear factor (erythroid-derived 2)-like 2 (Nrf2), additional studies investigated Fmo3 gene regulation by Nrf2 using Nrf2 knockout (Nrf2 KO) mice. At appropriate time-points, blood and liver samples were collected for assessment of plasma alanine aminotransferase (ALT) activity, plasma and hepatic bile acid levels, as well as liver Fmo3 mRNA and protein expression. Fmo3 mRNA expression increased significantly by 43-fold at 12 h after ANIT treatment, and this increase translates to a 4-fold change in protein levels. BDL also increased Fmo3 mRNA expression by 1899-fold, but with no change in protein levels. Treatment of mice with CCl4 decreased liver Fmo3 gene expression, while no change in expression was detected with AlOH treatment. Nrf2 KO mice are more susceptible to APAP (400 mg/kg, 72 h) treatment compared to their wild-type (WT) counterparts, which is evidenced by greater plasma ALT activity. The Fmo3 mRNA and protein expression increased in Nrf2 KO mice after APAP treatment. Collectively, not all hepatotoxicants that produce oxidative stress alter Fmo3 gene expression

  13. Determination of micronutrients and oxidative stress status in the blood of STZ-induced experimental diabetic rat models.

    Science.gov (United States)

    Ragbetli, Cennet; Dede, Semiha; Tanritanir, Pinar; Yoruk, Ibrahim Hakki; Ragbetli, Murat Cetin

    2014-11-01

    This study aims to research the effect of streptozotocin (STZ) at different doses on the serum micronutrients and oxidative stress status in diabetic rat models. Twenty male rats averaged 250 g and 3-4 months old were used as experimental models. They were put in four groups composed of five rats each. Diabetic was induced by administering STZ 55 and 65 mg/kg intraperitonally. The serum micronutrients including minerals and vitamins (Cu, Zn, Mg, Fe, vitamins D, E, and C) and oxidative stress (malondialdehyde, MDA) were determined. Cu, Zn, and Vitamin D3 levels were found to increase significantly in STZ groups (p micronutrients were affected significantly.

  14. A statistical model for estimating oxides of nitrogen emissions from light duty motor vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Fomunung, I; Washington, S.; Guensler, R. [Georgia Institute of Technology, Atlanta (United States). School of Civil and Environmental Engineering and Georgia Transportation Institute

    1999-09-01

    Motor vehicle emission rate models for predicting oxides of nitrogen (NOx) emissions are insensitive to vehicle modes of operation such as cruise, acceleration, deceleration, and idle, because they are based on average trip speed. Research has shown that NOx emissions are sensitive to engine load; hence, load-bases variables need to be included in emissions models. Ongoing studies attempting to incorporate these 'modal' variables have experienced difficulties with: (1) incomplete and/or non-representative data sets of emissions test data vis-a-vis the modal operating profiles of the tested vehicles; (2) lack of information for predicting on-road operating parameters of vehicles; and (3) non-representative vehicles recruited for emissions tests. The objective of this research was to develop a statistical model for predicting NOx emissions from light-duty gasoline motor vehicles. The primary end use of this model is forecasting, rather than explanation of the factor that affect NOx emissions, which brings us to bear different requirements from the statistical model. The three challenges noted above are addressed by: (1) analyzing a data set of more than 13,000 hot-stabilized laboratory treadmill tests on 19 driving cycles (specific speed versus time testing conditions), and 114 variables describing vehicle, engine and test cycle characteristics; (2) making the models compatible with empirical data on how vehicles are being operated in-use; and (3) developing statistical weights to account for the differences in model year distributions between the emissions testing database and the current national on-road fleets. The NOx emissions model is estimated using ordinary least-squares regression techniques, with transformed response variable and regression weights. Tree regression is employed as a tool for mining relationships among variables in the data, with particular focus on identifying useful interactions among discrete variables. Details of the model

  15. Sensorineural hearing loss and ischemic injury: Development of animal models to assess vascular and oxidative effects.

    Science.gov (United States)

    Olivetto, E; Simoni, E; Guaran, V; Astolfi, L; Martini, A

    2015-09-01

    Hearing loss may be genetic, associated with aging or exposure to noise or ototoxic substances. Its aetiology can be attributed to vascular injury, trauma, tumours, infections or autoimmune response. All these factors could be related to alterations in cochlear microcirculation resulting in hypoxia, which in turn may damage cochlear hair cells and neurons, leading to deafness. Hypoxia could underlie the aetiology of deafness, but very few data about it are presently available. The aim of this work is to develop animal models of hypoxia and ischemia suitable for study of cochlear vascular damage, characterizing them by electrophysiology and gene/protein expression analyses. The effects of hypoxia in infarction were mimicked in rat by partial permanent occlusion of the left coronary artery, and those of ischemia in thrombosis by complete temporary carotid occlusion. In our models both hypoxia and ischemia caused a small but significant hearing loss, localized at the cochlear apex. A slight induction of the coagulation cascade and of oxidative stress pathways was detected as cell survival mechanism, and cell damages were found on the cuticular plate of outer hair cells only after carotid ischemia. Based on these data, the two developed models appear suitable for in vivo studies of cochlear vascular damage. PMID:25987500

  16. Structural and vibrational study of graphene oxide via coronene based models: theoretical and experimental results

    Science.gov (United States)

    Almeida de Mendonça, João Paulo; Henrique de Lima, Alessandro; Amaral Junqueira, Georgia Maria; Gianini Quirino, Welber; Legnani, Cristiano; Oliveira Maciel, Indhira; Sato, Fernando

    2016-05-01

    We use the Coronene (C24H12), a simple and finite molecule, to make a model to study the spectroscopic and structural alterations generated by oxygenated groups in graphene oxide (GO). Based on the Lerf-Klinowski model, we chose the hydroxyl [OH-], the carboxyl [COOH-] and the epoxy [the ring C2O inside the molecule] as our radicals of interest and study their collective and isolated effects. We perform geometry optimization, vibrational IR (via AM1 and DFT-B3LYP) and Raman spectra (via DFT-B3LYP) of a series of functionalized coronene molecules. As results, we obtain some useful data for the analysis of IR and Raman spectra of GO, which facilitate the understanding and identification of the peaks found in the experiment. Finally, we suggest a new model to study GO, producing an accurate signature when compared to our experimental data. Such molecule shows in more details of the structural effects caused by functionalization when compared to experimental data.

  17. Controllable atomistic graphene oxide model and its application in hydrogen sulfide removal

    International Nuclear Information System (INIS)

    The determination of an atomistic graphene oxide (GO) model has been challenging due to the structural dependence on different synthesis methods. In this work we combine temperature-programmed molecular dynamics simulation techniques and the ReaxFF reactive force field to generate realistic atomistic GO structures. By grafting a mixture of epoxy and hydroxyl groups to the basal graphene surface and fine-tuning their initial concentrations, we produce in a controllable manner the GO structures with different functional groups and defects. The models agree with structural experimental data and with other ab initio quantum calculations. Using the generated atomistic models, we perform reactive adsorption calculations for H2S and H2O/H2S mixtures on GO materials and compare the results with experiment. We find that H2S molecules dissociate on the carbonyl functional groups, and H2O, CO2, and CO molecules are released as reaction products from the GO surface. The calculation reveals that for the H2O/H2S mixtures, H2O molecules are preferentially adsorbed to the carbonyl sites and block the potential active sites for H2S decomposition. The calculation agrees well with the experiments. The methodology and the procedure applied in this work open a new door to the theoretical studies of GO and can be extended to the research on other amorphous materials

  18. Biodistribution and imaging of fluorescently-tagged iron oxide nanoparticles in a breast cancer mouse model

    Science.gov (United States)

    Tate, Jennifer A.; Savellano, Mark D.; Hoopes, P. Jack

    2013-02-01

    Iron oxide nanoparticle (IONP) hyperthermia is an emerging treatment that shows great potential as a cancer therapy both alone and in synergy with conventional modalities. Pre-clinical studies are attempting to elucidate the mechanisms of action and distributions of IONP in various in vitro and in vivo models, however these studies would greatly benefit from real-time imaging of IONP locations both in cellular and in mammalian systems. To this end, fluorescently-tagged IONP (fIONP) have been employed for real time tracking and co-registration of IONP with iron content. Starch-coated IONP were fluorescently-tagged, purified and analyzed for fluorescent signal at various concentrations. fIONP were incubated with MTGB cells for varying times and cellular uptake analyzed using confocal microscopy, flow cytometry and inductively-coupled plasma mass spectrometry (ICP-MS). fIONP were also injected into a bilateral mouse tumor model for radiation modification of tumor tissue and enhanced fIONP deposition assessed using a Xenogen IVIS fluorescent imager. Results demonstrated that fIONP concentrations in vitro correlated with ICPMS iron readings. fIONP could be tracked in vitro as well as in tissue samples from an in vivo model. Future work will employ whole animal fluorescent imaging to track the biodistribution of fIONP over time.

  19. Global soil nitrous oxide emissions in a dynamic carbon–nitrogen model

    Directory of Open Access Journals (Sweden)

    Y. Y. Huang

    2015-02-01

    Full Text Available Nitrous oxide (N2O is an important greenhouse gas that also contributes to the depletion of stratospheric ozone. With high temporal and spatial heterogeneity, a quantitative understanding of terrestrial N2O emission, its variabilities and reponses to climate change is challenging. We added a soil N2O emission module to the dynamic global land model LM3V-N, and tested its sensitivity to soil moisture regime and responses to elevated CO2 and temperature. The model was capable of reproducing the average of cross-site observed annual mean emissions, although differences remained across individual sites if stand-level measurements were representative of gridcell emissions. Modelled N2O fluxes were highly sensitive to water filled pore space (WFPS, with a global sensitivity of approximately 0.25 Tg N year−1 per 0.01 change in WFPS. We found that the global response of N2O emission to CO2 fertilization was largely determined by the response of tropical emissions, whereas the extratropical response was weaker and different, highlighting the need to expand field studies in tropical ecosystems. Warming generally enhanced N2O efflux, and the enhancement was greatly dampened when combined with elevated CO2, although CO2 alone had a small effect. Our analysis suggests caution when extrapolation from current field CO2 enrichment and warming studies to the global scale.

  20. Simulation of nitrous oxide emissions at field scale using the SPACSYS model.

    Science.gov (United States)

    Wu, L; Rees, R M; Tarsitano, D; Zhang, Xubo; Jones, S K; Whitmore, A P

    2015-10-15

    Nitrous oxide emitted to the atmosphere via the soil processes of nitrification and denitrification plays an important role in the greenhouse gas balance of the atmosphere and is involved in the destruction of stratospheric ozone. These processes are controlled by biological, physical and chemical factors such as growth and activity of microbes, nitrogen availability, soil temperature and water availability. A comprehensive understanding of these processes embodied in an appropriate model can help develop agricultural mitigation strategies to reduce greenhouse gas emissions, and help with estimating emissions at landscape and regional scales. A detailed module to describe the denitrification and nitrification processes and nitrogenous gas emissions was incorporated into the SPACSYS model to replace an earlier module that used a simplified first-order equation to estimate denitrification and was unable to distinguish the emissions of individual nitrogenous gases. A dataset derived from a Scottish grassland experiment in silage production was used to validate soil moisture in the top 10 cm soil, cut biomass, nitrogen offtake and N2O emissions. The comparison between the simulated and observed data suggested that the new module can provide a good representation of these processes and improve prediction of N2O emissions. The model provides an opportunity to estimate gaseous N emissions under a wide range of management scenarios in agriculture, and synthesises our understanding of the interaction and regulation of the processes. PMID:26026411