WorldWideScience

Sample records for b4c oxidation modelling

  1. Anti-oxidation mechanism of SiC-B4C-C composites

    Institute of Scientific and Technical Information of China (English)

    LIU Qi-cheng; XU Xie-wen; HUANG Qi-zhong; HUANG Bai-yun

    2005-01-01

    Mixture of green petroleum coke, B4C and SiC together with short carbon fiber were employed as starting materials, the mixture was press-formed without any binder after grinding, dense and homogeneous binderless SiC-B4C-C(carbon/ceramic) composites were then obtained after sintering. Composites thus prepared possess excellent anti-oxidation property, that is, mass loss less than 1% within the temperature range from 900 to 1100℃ for 10h. Anti-oxidation mechanism was also discussed from the viewpoint of thermodynamics, excellent anti-oxidation property of materials thus prepared can be discribed to 1) solid SiO2 formed from SiC, which restrains the filtering of oxygen and simultaneously, its volume expansion brought about by the reaction takes roles both walling up the original pores and making the material more compact; 2) liquid B2O3 from the reaction of B4C not only makes the combination with C, B4C and SiC tighter through forming solid solution, but also effect of reaction SiC(s)+2CO(g)=SiO2(s)+3C(s) is an expansive process, which improves the microstructure of the material.

  2. 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.

  3. PARTICLE SIZE-DEPENDENT PULVERIZATION OF B4C AND GENERATION OF B4C/STS NANOPARTICLES USED FOR NEUTRON ABSORBING COMPOSITES

    Directory of Open Access Journals (Sweden)

    JAEWOO KIM

    2014-10-01

    Full Text Available Pulverization of two different sized micro-B4C particles (∼10 μm and ∼150 μm was investigated using a STS based high energy ball milling system. Shapes, generation of the impurities, and reduction of the particle size dependent on milling time and initial particle size were investigated using various analytic tools including SEM-EDX, XRD, and ICP-MS. Most of impurity was produced during the early stage of milling, and impurity content became independent on the milling time after the saturation. The degree of particle size reduction was also dependent on the initial B4C size. It was found that the STS nanoparticles produced from milling is strongly bounded with the B4C particles forming the B4C/STS composite particles that can be used as a neutron absorbing nanocomposite. Based on the morphological evolution of the milled particles, a schematic pulverization model for the B4C particles was constructed.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Inhibitor effects of sodium benzoate on corrosion resistance of Al6061-B4C composites in NaCl and H3BO3 solutions

    Science.gov (United States)

    Rafi-ud-din; Shafqat, Q. A.; Shahzad, M.; Ahmad, Ejaz; Asghar, Z.; Rafiq, Nouman; Qureshi, A. H.; Syed, Waqar adil; asim Pasha, Riffat

    2016-12-01

    Sodium benzoate (SB) is used for the first time to inhibit the corrosion of Al6061-B4C composites in H3BO3 and NaCl solutions. Al6061100-x -x wt% B4C (x = 0, 5, and 10) composites are manufactured by a powder metallurgy route. The corrosion inhibition efficiency of SB is investigated as a function of the volume fractions of B4C particles by using potentiodynamic polarization and electrochemical impedance techniques. Without the use of an inhibitor, an increase of the B4C particles in the composite decreases the corrosion resistance of Al6061-B4C composites. It is found that SB is an efficient corrosion inhibitor for Al6061-B4C composites in both investigated solutions. The corrosion inhibition efficiency of SB increases with an increase in B4C content. Since SB is an adsorption type inhibitor, it is envisaged that an extremely thin layer of molecules adsorbs onto the surface and suppresses the oxidation and reduction. It is found that the inhibitor effect of SB is more pronounced in a H3BO3 environment than in NaCl solution. Further, the mechanism of corrosion inhibition by SB is illustrated by using optical and scanning electron microscopy of corroded samples. It is found that the adsorption of benzoate ions on the Al surface and its bonding with Al3+ ions forms a hydrophobic layer on top of the exposed Al surface, which enhances the protection against dissolved boride ions.

  9. 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.

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

    Science.gov (United States)

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

    2016-03-01

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

  11. 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.

  12. Thermally induced decomposition of B4C barrier layers in Mo/Si multilayer structures

    NARCIS (Netherlands)

    Bruijn, S.; van de Kruijs, R. W. E.; Yakshin, A. E.; Zoethout, E.; F. Bijkerk,

    2010-01-01

    We investigate the influence of the Mo crystalline state (quasi-amorphous or crystalline) on the thermal stability of Mo/Si thin film multilayers with B4C diffusion barrier layers at either of the two interfaces. We find that multilayers containing amorphous Mo layers are more stable than those cont

  13. 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.

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

    Science.gov (United States)

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

    2015-01-01

    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.

  15. B4C protective coating under irradiation by QSPA-T intensive plasma fluxes

    Science.gov (United States)

    Buzhinskij, O. I.; Barsuk, V. A.; Begrambekov, L. B.; Klimov, N. S.; Otroshchenko, V. G.; Putric, A. B.

    2016-12-01

    The effect of the QSPA-T pulsed plasma irradiation on the crystalline boron carbide B4C coating was examined. The duration of the rectangular plasma pulses was 0.5 ms with an interval of 5-10 min between pulses. The maximum power density in the central part of plasma stream was 1 GW/m2. The coating thickness varied from 20 to 40 μm on different surface areas. Modification of the surface layers and transformation of the coating at elevated temperature under plasma pulse irradiation during four successive series of impulses are described. It is shown that the boron carbide coating withstood the full cycle of tests under irradiation with 100 plasma pulses with peak power density of 1GW/m2. Constitutive surface deterioration was not detected and the boron carbide coating kept crystal structure B4C throughout the irradiation zone at the surface depth no less 2 μm.

  16. 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.

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

    DEFF Research Database (Denmark)

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

    1995-01-01

    The loss of throughput observed at higher energies for traditional grazing-incidence X-ray telescopes coated with high-Z elements can be partly countered by employing multilayers on the outermost reflectors. Using 8-keV reflectivity data from a periodic W/B4C multilayer, the expected performance ...... reflectors required by the Kirkpatrick-Baez telescope exists, so that an Fe-line multilayer telescope could be built today...

  18. 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.

  19. Evaluation of drilling Al/B4C composites with carbide drills

    Directory of Open Access Journals (Sweden)

    Ali Rıza Motorcu

    2016-08-01

    Full Text Available In this study, cutting forces and torque was evaluated through Taguchi Method (TM in the drilling of the high density B4C particle reinforced composites, which were produced through powder metallurgy-hot pressing method, with coated and uncoated carbide drills. Cutting speed (18, 25 and 35 m/min, feed rate (0.08, 0.112 and 0.16 mm/rev, coating properties (coated and uncoated and the amounts of particle reinforcement (5%, 10% and 15% B4C were used as the control factors. It was observed that the increased feed rate and particle reinforcement increased the axial force and torque, and decreased the cutting speed. The uncoated drills had a better performance than the coated drills. The amount of B4C reinforcement was observed to be the most effective parameter on the axial force and torque with the contribution ratios of 96.6% and 49.1%, respectively. Moreover, the correlation coefficients (R2 of the first order predictive equations developed for the axial force and torque were calculated as 0.895 and 0.854, respectively.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries

    Energy Technology Data Exchange (ETDEWEB)

    Song, Shidong; Xu, Wu; Cao, Ruiguo; Luo, Langli; Engelhard, Mark H.; Bowden, Mark E.; Liu, Bin; Estevez, Luis; Wang, Chong-Min; Zhang, Ji-Guang

    2017-01-19

    Lithium-oxygen (Li-O2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B4C) as the non-carbon based oxygen electrode material for aprotic Li-O2 batteries. B4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable for battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B4C based electrode is mainly due to be the loss of active sites on B4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B4C is a very promising alternative oxygen electrode material for aprotic Li-O2 batteries. It can also be used as a standard electrode to investigate the stability of electrolytes.

  5. Formation of Al/B4C Surface Nano-composite Layers on 7075 Al Alloy Employing Friction Stir Processing

    Science.gov (United States)

    Kashani-Bozorg, S. F.; Jazayeri, K.

    2009-06-01

    Al/B4C surface nano-composite layers was achieved on commercial 7075 Al substrate employing friction stir processing technique. Agglomeration of B4C particles was occurred after a single pass. The dispersion of B4C particles was found to be affected by the number of FSP passes. A distribution of nano-size B4C particle was achieved after four passes. Moreover, the increasing in number of FSP passes causes a decreasing in matrix grain size of the surface nano-composite layer. The micro hardness of the surface nano-composite layer improves by almost two times as compared to that of the as-received substrate; this is attributed to the finer matrix grains and dispersion of nano-sized B4C particles.

  6. 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.

  7. 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.

  8. 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.

  9. 热压法制备高含量B4C/铝基复合材料的显微结构与力学性能%Microstructure and mechanical properties of high content B4C-aluminium composites fabricated by hot-pressing sintering

    Institute of Scientific and Technical Information of China (English)

    张鹏; 张哲维; 李宇力; 王文先; 王保东

    2014-01-01

    采用低温真空热压法制备B4C质量分数为30%、平均粒度为23μm的B4C/Al基复合材料,热压温度控制在基体6061Al合金的固液相线之间。对B4C/Al复合材料进行显微结构分析和力学性能检测,结果表明:B4C/Al复合材料内无大尺寸的显微缺陷,组织分布较均匀、致密,界面结合较好;B4C/Al基复合材料的硬度比基体6061铝合金提高34.9%,断裂韧性是B4C增强颗粒断裂韧性的5.16倍,屈服强度比基体提高198.3%。利用Ramakrishnan提出的金属基复合材料屈服强度的分析模型,对30%B4C/Al复合材料的屈服强度进行计算,计算结果与实验结果基本符合。分析表明微米级B4C颗粒对6061Al合金的增强机制主要为载荷增强和位错增强。%30%B4C (mass fraction) particle-reinforcing Al matrix composite with the average particle size 23μm of was prepared by low temperature vacuum hot-pressing technique. The preparation temperature was between the solid and liquid phase line of the 6061Al matrix. The microstructure and mechanical property were analyzed. The results show that the particles are uniformly distributed in the B4C/Al composite without agglomeration and there is mutual diffusion between the particles and matrix. The interface bonds between matrix and reinforcer well. The hardness of B4C/Al composite is 34.9%higher than that of 6061 aluminum alloy. The fracture toughness of B4C/Al composite is 5.16 times larger than that of the B4C material and the yield strength increases 198.3%than that of the matrix. An analytical model for the strength of metal matrix composites presented by Ramakrishnan was selected to calculate the yield strength of the 30%B4C/Al composite. The results of theoretical calculations agree well with the experimental data. The strengthening mechanisms of B4C particle-reinforcing Al matrix composite with micron particle size are mainly loading strengthening and dislocation strengthening.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Fatigue performance and fracture mechanism of B4C/6061Al composites%B4C/6061铝基复合材料疲劳性能及断裂机制

    Institute of Scientific and Technical Information of China (English)

    秦艳兵; 王文先; 李宇力; 张鹏; 王保东

    2014-01-01

    基于轻质、高强和耐磨等诸多优势,铝基碳化硼复合材料已成为集结构/功能一体化的新型材料。本文采用粉末冶金及轧制方法,制备出厚度3.5 mm、碳化硼质量分数为33%的B4C/Al复合材料板材,并对其疲劳性能和断裂机制进行分析。在1×107循环次数下,铝基碳化硼复合材料板材的疲劳强度达到110 MPa。采用SEM对疲劳断口进行观察,结果表明B4C/Al复合材料疲劳断口可清楚的看到裂纹的萌生、扩展和失稳断裂的典型特征,但存在多种形式的疲劳启裂源。疲劳裂纹扩展路径取决于裂纹尖端塑性区的半径和B4C颗粒的间距大小,当增强颗粒的间距小于塑性区半径时,裂纹主要沿着颗粒的连接界面或断裂的碳化硼颗粒扩展,当增强颗粒的间距大于塑性区半径时,有利于裂纹尖端钝化,减缓裂纹的扩展和方向改变。%With the advantages of low density, high strength and wear resistance, etc, the aluminum matrix composite reinforced by ceramic particles has became a new material which integrating structure and function. The B4C/Al composite with mass fraction of 33% of boron carbide and the plates of thickness 3.5 mm were manufactured by powder metallurgy and rolling. The fatigue performance and fracture mechanism of B4C/Al composite were studied. Fatigue experiment concludes that the fatigue limit of B4C/Al composite is 110 MPa under 1×107 fatigue cycles. SEM and EDS were used to observe the fatigue fracture and analyze the fracture points. The characteristics of crack initiation, crack propagation, unstability to breakdown were found on the fatigue fracture surface, and different kinds of fatigue source exist in the B4C/Al composite; The fatigue crack extension path of B4C/aluminium composites with a high content of boron carbide depends on the particle interval of B4C and radius of the crack tip plastic zone. When the radius of crack tip is bigger than the

  16. 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.

  17. 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.

  18. 高含量B4C/Al基复合材料磨损行为研究%Adhesive Wear Behavior of High Content B4C-Aluminium Metal Matrix Composite

    Institute of Scientific and Technical Information of China (English)

    张鹏; 张哲维; 陈洪胜; 王文先; 王保东

    2014-01-01

    对质量分数分别为20%、30%和40%的高含量B4C/Al基复合材料的磨损行为进行了研究,分析了颗粒含量、载荷变化以及磨损时间对该复合材料磨损性能的影响,探索了该复合材料磨损过程的微观机制.结果表明:B4C/Al基复合材料的磨擦系数随B4C含量的增加而减小,材料耐磨损性能随B4C硬质颗粒含量的增加而提高;随载荷从30 N增加到70 N,B4C/Al复合材料的磨擦系数先减小再增加,材料磨损速率随载荷增加而增大.随磨损进行,整个磨损过程体现出阶段性的变化,复合材料的摩擦系数先减小再增加,磨损速率先缓慢增大,然后较快增长.高含量B4C/Al基复合材料磨损过程主要表现为犁削磨损和黏着磨损的磨损方式,同时还伴随有氧化磨损机制.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. On the Prospects of Using Nanoindentation and Wear Test to Study the Mechanical Behavior of Fe-Based Metallic Glass Coating Reinforced by B4C Nanoparticles

    Science.gov (United States)

    Movahedi, Behrooz

    2017-01-01

    In this study, Fe-based metallic glass was served as the matrix in which various ratios of hard B4C nanoparticles as reinforcing agents were prepared using a high-energy mechanical milling. The feedstock nanocomposite powders were transferred to the coatings using a high-velocity oxygen fuel process. The results showed that the microstructure of the nanocomposite coating was divided into two regions, namely a full amorphous phase region and homogeneous dispersion of B4C nanoparticles with a scale of 10 to 50 nm in a residual amorphous matrix. As the B4C content is increased, the hardness of the composite coatings is increased too, but the fracture toughness begins to be decreased at the B4C content higher than 20 vol pct. The optimal mechanical properties are obtained with 15 vol pct B4C due to the suitable content and uniform distribution of nanoparticles. The addition of 15 vol pct B4C to the Fe-based metallic glass matrix reduced the friction coefficient from 0.49 to 0.28. The average specific wear rate of the nanocomposite coating (0.48 × 10-5 mm3 Nm-1) was much less than that for the single-phase amorphous coating (1.23 × 10-5 mm3Nm-1). Consequently, the changes in wear resistance between both coatings were attributed to the changes in the brittle to ductile transition by adding B4C reinforcing nanoparticles.

  7. On the Prospects of Using Nanoindentation and Wear Test to Study the Mechanical Behavior of Fe-Based Metallic Glass Coating Reinforced by B4C Nanoparticles

    Science.gov (United States)

    Movahedi, Behrooz

    2017-03-01

    In this study, Fe-based metallic glass was served as the matrix in which various ratios of hard B4C nanoparticles as reinforcing agents were prepared using a high-energy mechanical milling. The feedstock nanocomposite powders were transferred to the coatings using a high-velocity oxygen fuel process. The results showed that the microstructure of the nanocomposite coating was divided into two regions, namely a full amorphous phase region and homogeneous dispersion of B4C nanoparticles with a scale of 10 to 50 nm in a residual amorphous matrix. As the B4C content is increased, the hardness of the composite coatings is increased too, but the fracture toughness begins to be decreased at the B4C content higher than 20 vol pct. The optimal mechanical properties are obtained with 15 vol pct B4C due to the suitable content and uniform distribution of nanoparticles. The addition of 15 vol pct B4C to the Fe-based metallic glass matrix reduced the friction coefficient from 0.49 to 0.28. The average specific wear rate of the nanocomposite coating (0.48 × 10-5 mm3 Nm-1) was much less than that for the single-phase amorphous coating (1.23 × 10-5 mm3Nm-1). Consequently, the changes in wear resistance between both coatings were attributed to the changes in the brittle to ductile transition by adding B4C reinforcing nanoparticles.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. An Experimental Investigation of Effects of Fluxes (Na3AlF6 and K2TiF6), Element Alloys (Mg), and Composite Powders ((Al + TiC)CP and (Al + B4C)CP) on Distribution of Particles and Phases in Al-B4C and Al-TiC Composites

    Science.gov (United States)

    Mazaheri, Younes; Emadi, Rahmatollah; Meratian, Mahmood; Zarchi, Mehdi Karimi

    2017-04-01

    The wettability, incorporation, and gravity segregation of TiC and B4C particles into molten aluminum are important problems in the production of Al-TiC and Al-B4C composites by the casting techniques. In order to solve these problems, different methods consisting of adding the Na3AlF6 and K2TiF6 fluxes and Mg (as the alloying element) into the molten aluminum and injection of the (Al + TiC)CP and (Al + B4C)CP composite powders instead of B4C and TiC particles are evaluated. In this work, the conditions of sample preparation, such as particle addition temperature, stirring speed, and stirring time, are determined after many studies and tests. Microstructural characterizations of samples are investigated by scanning electron microscopy equipped with energy dispersive spectroscopy (EDS) and X-ray diffractometry. The results show better distribution and incorporation of TiCp and B4Cp in aluminum matrix when the fluxes are used, as well as EDS analysis of the interface between the matrix and reinforcement-strengthened formation of the different phases such as Al4C3 in the Al-TiC composites and Al3BC, TiB2 in the Al-B4C composites.

  18. An Experimental Investigation of Effects of Fluxes (Na3AlF6 and K2TiF6), Element Alloys (Mg), and Composite Powders ((Al + TiC)CP and (Al + B4C)CP) on Distribution of Particles and Phases in Al-B4C and Al-TiC Composites

    Science.gov (United States)

    Mazaheri, Younes; Emadi, Rahmatollah; Meratian, Mahmood; Zarchi, Mehdi Karimi

    2017-01-01

    The wettability, incorporation, and gravity segregation of TiC and B4C particles into molten aluminum are important problems in the production of Al-TiC and Al-B4C composites by the casting techniques. In order to solve these problems, different methods consisting of adding the Na3AlF6 and K2TiF6 fluxes and Mg (as the alloying element) into the molten aluminum and injection of the (Al + TiC)CP and (Al + B4C)CP composite powders instead of B4C and TiC particles are evaluated. In this work, the conditions of sample preparation, such as particle addition temperature, stirring speed, and stirring time, are determined after many studies and tests. Microstructural characterizations of samples are investigated by scanning electron microscopy equipped with energy dispersive spectroscopy (EDS) and X-ray diffractometry. The results show better distribution and incorporation of TiCp and B4Cp in aluminum matrix when the fluxes are used, as well as EDS analysis of the interface between the matrix and reinforcement-strengthened formation of the different phases such as Al4C3 in the Al-TiC composites and Al3BC, TiB2 in the Al-B4C composites.

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

    Directory of Open Access Journals (Sweden)

    Alireza Abdollahi

    2014-12-01

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

  20. 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.

  1. 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.

  2. 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.

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

    Directory of Open Access Journals (Sweden)

    Mengxian Zhang

    2015-09-01

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

  4. 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.

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

    Science.gov (United States)

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

    2016-09-01

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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. B4C含量对B4C增强Ni基合金钎涂层的影响%Influence of Content of B4C on the Hardness of Braze Coating of the B4C/Nickel-base Powders Composite Coatings

    Institute of Scientific and Technical Information of China (English)

    侯立宁

    2012-01-01

    为提高低碳钢的表面性能,以Ni基合金为原材料,添加一定量的B4C粉末作增强相,钎涂于低碳钢表面,研究了B4C添加量对涂层性能的影响.结果表明:控制合理的工艺参数,可以获得表面平整、光滑,与基体呈冶金结合的涂层;随着B4C添加量的增加,涂层的硬度及耐磨性也逐渐增加,但添加量增加到一定值后,涂层与基体的熔合效果不佳,出现气孔等缺陷,硬度及耐磨性反而下降.%In order to improve the surface properties of low carbon steel, Ni-base powders added certain amount of B4C were surface brazed on low-carbon steel. On the basis the effect of content of B4C on the performance of coatings was studied. The result shows that the smooth surface can be formed under reasonable control of the process parameters and the coating integrated with the substrate together well by metallurgical bonding; Moreover, with the increasing of the quality score of B4C particle in nickel-based alloys, the hardness and wear resistance of the coating is gradually increasing at the first, but to a certain percentage, the metallurgical combine effect is becoming poor at the same time existing some defects such as pore, furthermore the hardness and wear resistance decline.

  12. 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.

  13. Study on (W + B4C)/Al composites of neutron shielding properties based on monte carlo simulation%(W+B4C)/Al复合材料中子屏蔽性能的蒙特卡罗模拟

    Institute of Scientific and Technical Information of China (English)

    王健; 马书旺; 杨剑; 梁秋实; 刘坤; 杨志民; 毛昌辉

    2016-01-01

    使用MCNP5程序模拟了能量为14.88 MeV的快中子在(W +B4C)/Al和W/Al复合材料中的输运过程,并与铅硼聚乙烯、聚乙烯以及钨进行对比.计算了各屏蔽材料的中子衰减性能、中子透射能谱以及中子俘获过程中释放γ射线的透射能谱,为中子屏蔽材料的选择提供了理论依据.模拟结果和实际结果吻合,证实了蒙特卡罗方法的可靠性.模拟结果也可以得出,对于快中子,高原子序数材料的屏蔽效果要好于低原子序数材料,含钨45%的复合材料的屏蔽性能与商用铅硼聚乙烯的屏蔽效能相近,但是激发γ射线能量低于铅硼聚乙烯,考虑到成分可调控性、使用温度以及力学性能等因素,(W+ B4C)/A1复合材料是一种极具应用潜力的新型中子屏蔽材料.%The transmission process of (W + B4C)/A1 and W/A1 composites with 14.88 MeV neutron energy was simulated by MCNP5 program and compared with those of lead-born carbide-polyethylene,polyethylene and tungsten.The estimations of neutron attenuation,neutron transmission spectrum and γ transmission spectra induced by neutron capture process provided the theoretical basis of selecting neutron shielding materials.The simulative results were basically consistent with those observed in practice,confirming the reliability of Monte Carlo methods.The results showed that high atomic number materials had a better performance in fast neutron shielding than that of low atomic number materials.The shielding properties of composites with 45% W content were closed to that of commercial lead-born carbide-polyethylene with lower γ energy induced by neutron capturing.With the properties of component adjustment,using temperatures and mechanical behavior,(W + B4C)/Al composite is a new type of neutron shielding material with great potential application.

  14. 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。

  15. Effect of Ti Addition on the Residual Aluminium Content and Mechanical Properties of the B4C-Al Composites Produced by Vacuum Infiltration / Wpływ Dodatku Tytanu Na Resztkową Zawartość Aluminium I Właściwości Mechaniczne Kompozytów B4C-Al Wytworzonych Przez Infiltrację Próżniową

    Directory of Open Access Journals (Sweden)

    Xiaozhou Cao

    2015-12-01

    Full Text Available The effect of Ti addition on the residual Al content and mechanical properties of B4C-Al composites fabricated by vacuum infiltration was investigated in the present study. The B4C-Al composite materials were fabricated using [Ti+B4C] preforms preheated at 1700ºC for 1 h and Al alloys infiltrated in vacuum atmosphere at 1100ºC for 2 h. The phase composition indicated that TiB2 has high wettability to Al as a result of the preheating. SEM and EDX results revealed a number of Al dimples are on the fracture surface due to the existence of TiB2. When the content of added Ti increases to 30%, the [Ti+B4C] preform is characterized by a minimal porosity (33.11% and a maximal density, a corresponding amount of residual Al of 33.11% and a minimal fracture toughness (5.03 MPa·m1/2 with a hardness of up to 63 HRC. The residual Al and the mechanical properties of the composite material preform were determined by the Ti content of the preform.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Effect of nano/micro B4C and SiC particles on fracture properties of aluminum 7075 particulate composites under chevron-notch plane strain fracture toughness test

    Science.gov (United States)

    Morovvati, M. R.; Lalehpour, A.; Esmaeilzare, A.

    2016-12-01

    Reinforcing aluminum with SiC and B4C nano/micro particles can lead to a more efficient material in terms of strength and light weight. The influence of adding these particles to an aluminum 7075 matrix is investigated using chevron-notch fracture toughness test method. The reinforcing factors are type, size (micro/nano), and weight percent of the particles. The fracture parameters are maximum load, notch opening displacement, the work up to fracture and chevron notch plane strain fracture toughness. The findings demonstrate that addition of micro and nano size particles improves the fracture properties; however, increasing the weight percent of the particles leads to increase of fracture properties up to a certain level and after that due to agglomeration of the particles, the improvement does not happen for both particle types and size categories. Agglomeration of particles at higher amounts of reinforcing particles results in improper distribution of particles and reduction in mechanical properties.

  1. Influence of additives on oxidation resistance of binderless C/C composite

    Institute of Scientific and Technical Information of China (English)

    周声劢; 刘其城; 胡晓凯

    2003-01-01

    Experiment of adding B4C, SiC, and Si powders to improve oxidation resistance of the C/C compositeswas carried out. The results show that the increase of oxidation resistance is remarkable when the contents of B4C,SiC, and Si powders are 10%, 10%, and 5% in the composites, respectively. The regularities and mechanism ofthe effects of the ceramic powders on the oxidation resistance of the composites were also discussed.

  2. 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.

  3. Advanced oxidation processes: overall models

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-07-01

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

  4. 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.

  5. 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

  6. 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.

  7. Empirical Modeling of Metal Oxides Dissolution

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seon-Byeong; Won, Hui-Jun; Park, Sang-Yoon; Moon, Jei-Kwon; Choi, Wang-Kyu [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    There have been tons of studies to examine the dissolution of metal oxides in terms of dissolution kinetics, type of reactants, geometry, etc. However, most of previous studies is the observation of macroscopic dissolution characteristics and might not provide the atomic scale characteristics of dissolution reactions. Even the analysis of microscopic structure of metal oxide with SEM, XRD, etc. during the dissolution does not observe the microscopic characteristics of dissolution mechanism. Computational analysis with well-established dissolution model is the one of the best approaches to understand indirectly the microscopic dissolution behaviour. Various designs of experimental conditions are applied to the in-vitro methods interpreting the dissolution characteristics controlled by each influencing parameter.

  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. Modeling Nitrogen Oxides in the Lower Stratosphere

    Science.gov (United States)

    Kawa, S. Randy; Einaudi, Franco (Technical Monitor)

    2001-01-01

    This talk will focus on the status of current understanding (not a historical review) as regards modeling nitrogen oxides (NOy) in the lower stratosphere (LS). The presentation will be organized around three major areas of process understanding: 1) NOy sources, sinks, and transport to the LS, 2) NOy species partitioning, and 3) polar multiphase processes. In each area, process topics will be identified with an estimate of the degree of confidence associated with their representation in numerical models. Several exotic and/or speculative processes will also be discussed. Those topics associated with low confidence or knowledge gaps, weighted by their prospective importance in stratospheric chemical modeling, will be collected into recommendations for further study. Suggested approaches to further study will be presented for discussion.

  10. Simulation of wet oxidation of silicon based on the interfacial silicon emission model and comparison with dry oxidation

    OpenAIRE

    Uematsu, Masashi; Kageshima, Hiroyuki; Shiraishi, Kenji

    2001-01-01

    Silicon oxidation in wet ambients is simulated based on the interfacial silicon emission model and is compared with dry oxidation in terms of the silicon-atom emission. The silicon emission model enables the simulation of wet oxidation to be done using the oxidant self-diffusivity in the oxide with a single activation energy. The amount of silicon emission from the interface during wet oxidation is smaller than that during dry oxidation. The small emission rate for wet oxidation is responsibl...

  11. 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.

  12. Simplified Modeling of Oxidation of Hydrocarbons

    Science.gov (United States)

    Bellan, Josette; Harstad, Kenneth

    2008-01-01

    A method of simplified computational modeling of oxidation of hydrocarbons is undergoing development. This is one of several developments needed to enable accurate computational simulation of turbulent, chemically reacting flows. At present, accurate computational simulation of such flows is difficult or impossible in most cases because (1) the numbers of grid points needed for adequate spatial resolution of turbulent flows in realistically complex geometries are beyond the capabilities of typical supercomputers now in use and (2) the combustion of typical hydrocarbons proceeds through decomposition into hundreds of molecular species interacting through thousands of reactions. Hence, the combination of detailed reaction- rate models with the fundamental flow equations yields flow models that are computationally prohibitive. Hence, further, a reduction of at least an order of magnitude in the dimension of reaction kinetics is one of the prerequisites for feasibility of computational simulation of turbulent, chemically reacting flows. In the present method of simplified modeling, all molecular species involved in the oxidation of hydrocarbons are classified as either light or heavy; heavy molecules are those having 3 or more carbon atoms. The light molecules are not subject to meaningful decomposition, and the heavy molecules are considered to decompose into only 13 specified constituent radicals, a few of which are listed in the table. One constructs a reduced-order model, suitable for use in estimating the release of heat and the evolution of temperature in combustion, from a base comprising the 13 constituent radicals plus a total of 26 other species that include the light molecules and related light free radicals. Then rather than following all possible species through their reaction coordinates, one follows only the reduced set of reaction coordinates of the base. The behavior of the base was examined in test computational simulations of the combustion of

  13. Mathematical Model of Silicon Oxidation in Microelectronics

    Directory of Open Access Journals (Sweden)

    V. A. Bondarev

    2006-01-01

    Full Text Available The paper involves analytical solutions and formulae for determination of the oxide film thickness in the silicon oxidation while using nitride mask. Calculations are based on solutions of a three-dimensional diffusion equation and new mathematical functions that are firstly defined by the author. Suitable analytical and numerical solutions based on the diffusion equation have not yet been obtained

  14. Modeling for CVD of Solid Oxide Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Starr, T.L.

    2002-09-18

    Because of its low thermal conductivity, high thermal expansion and high oxygen ion conductivity yttria-stabilized zirconia (YSZ) is the material of choice for high temperature electrolyte applications. Current coating fabrication methods have their drawbacks, however. Air plasma spray (APS) is a relatively low-cost process and is suitable for large and relatively complex shapes. it is difficult to produce uniform, relatively thin coatings with this process, however, and the coatings do not exhibit the columnar microstructure that is needed for reliable, long-term performance. The electron-beam physical vapor deposition (EB-PVD) process does produce the desirable microstructure, however, the capital cost of these systems is very high and the line-of-sight nature of the process limits coating uniformity and the ability to coat large and complex shapes. The chemical vapor deposition (CVD) process also produces the desirable columnar microstructure and--under proper conditions--can produce uniform coatings over complex shapes. CVD has been used for many materials but is relatively undeveloped for oxides, in general, and for zirconia, in particular. The overall goal of this project--a joint effort of the University of Louisville and Oak Ridge National Laboratory (ORNL)--is to develop the YSZ CVD process for high temperature electrolyte applications. This report describes the modeling effort at the University of Louisville, which supports the experimental work at ORNL. Early work on CVD of zirconia and yttria used metal chlorides, which react with water vapor to form solid oxide. Because of this rapid gas-phase reaction the water generally is formed in-situ using the reverse water-gas-shift reaction or a microwave plasma. Even with these arrangements gas-phase nucleation and powder formation are problems when using these precursors. Recent efforts on CVD of zirconia and YSZ have focused on use of metal-organic precursors (MOCVD). These are more stable in the gas

  15. A Detailed Modeling Study of Propane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Jayaweera, T M; Pitz, W J; Curran, H J

    2004-03-19

    A detailed chemical kinetic mechanism has been used to simulate ignition delay times recorded by a number of experimental shock tube studies over the temperature range 900 {le} T {le} 1800 K, in the pressure range 0.75-40 atm and in the equivalence ratio range 0.5 {le} {phi} {le} 2.0. Flame speed measurements at 1 atm in the equivalence ratio range 0.4 {le} {phi} {le} 1.8 have also been simulated. Both of these data sets, particularly those recorded at high pressure, are of particular importance in validating a kinetic mechanism, as internal combustion engines operate at elevated pressures and temperatures and rates of fuel oxidation are critical to efficient system operation. Experiments in which reactant, intermediate and product species were quantitatively recorded, versus temperature in a jet-stirred reactor (JSR) and versus time in a flow reactor are also simulated. This data provide a stringent test of the kinetic mechanism as it must reproduce accurate quantitative profiles for all reactant, intermediate and product species. The JSR experiments were performed in the temperature range 1000-1110 K, in the equivalence ratio range 0.5 {le} {phi} {le} 4.0, at a pressure of 5 atm. These experiments are complemented by those carried out in a flow reactor in the temperature range 660-820 K, at 10 atm and at an equivalence ratio of 0.4. In addition, burner stabilized flames were simulated, where chemical species profiles were measured at atmospheric pressure for two propane-air flat flames. Overall, reasonably good agreement is observed between the model simulations and the experimental results.

  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. Air oxidation of Zircaloy, Part 2: New model for Zry-4 oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Stempniewicz, M.M., E-mail: stempniewicz@nrg.eu

    2016-05-15

    Highlights: • Recommended set of correlations proposed for air oxidation of Zircaloy-4. • New breakaway correlation for air oxidation of Zircaloy-4. • Improved accuracy of predicting air oxidation of Zircaloy-4. • Models applicable to analyses of accidents in Spent Fuel Pool. - Abstract: The accident in Fukushima brought up new issues in the area of safety of nuclear reactors. Among others, Spent Fuel Pool accidents gained new focus. The computer codes applicable for safety analyses of Nuclear Power Plants have limited verification and validation in this area and their applicability remains still to be proven. An important phenomenon occurring during loss of water in SFP is air oxidation of Zircaloy cladding material. Mathematical modeling of this phenomenon in computer codes has been under development during the last years. This document presents a review of models for air oxidation of Zircaloy, including: up to date models available in open literature, as well as models available in computer codes: ASTEC, MELCOR, and SPECTRA. The models were tested by performing simulations of a number air oxidation experiments from ANL, KIT, and IRSN. As a result of this work, a recommended set of correlations, applicable for wide range of temperatures, including pre- and post-breakaway reaction, has been selected. For the pre-breakaway (parabolic) regime the correlation of Benjamin et al. (Sandia National Laboratories, Albuquerque, NM, 1979) was selected for the low temperatures and a new correlation has been proposed for the high temperatures. For the post-breakaway (linear) regime, Boase and Vandergraaf (Nucl. Technol., 1977;32:60–71) were selected for the low temperatures and a new correlation has been proposed for the high temperatures. Furthermore, a new model for the breakaway transition has been proposed. The correlation set is applicable for Zircaloy-4, for practically the entire temperature range. The recommended set provides an improved accuracy of results

  18. Effects of Oxidation on Oxidation-Resistant Graphite

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-01

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

  19. 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.

  20. 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...

  1. 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...

  2. 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

  3. 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.

  4. Study of influence content of TiB{sub 2} by reaction in situ B{sub 4}C and TiC in mechanical properties on B4C ceramics; Estudo da infuencia do teor de TIB{sub 2}, obtido pela reacao in sutu de B{sub 4}C de TiC, nas propriedades mecanicas de ceramicas a base de B{sub 4}C

    Energy Technology Data Exchange (ETDEWEB)

    Coelho, M.L. Ramos; Bressiani, J.C. [Instituto de Pesquisa Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Gomide, R.G.; Andrade, F.A. de, E-mail: maluraco@usp.br, E-mail: gomide@ctmsp.mar.mil.br, E-mail: fernando.andrade@ctmsp.mar.mil.br, E-mail: jbressia@ipen.br [Centro Tecnologico da Marinha em Sao Paulo (CTMS), Sao Paulo, SP (Brazil)

    2012-07-01

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

  5. Alternative model for the Great Oxidation Event

    Science.gov (United States)

    Bekker, A.

    2014-12-01

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

  6. Subcritical and supercritical water oxidation of CELSS model wastes

    Science.gov (United States)

    Takahashi, Y.; Wydeven, T.; Koo, C.

    1989-01-01

    A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

  7. Modeling the ignition of a copper oxide aluminum thermite

    Science.gov (United States)

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

    2017-01-01

    An experimental "striker confinement" shock compression experiment 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. Sample of materials such as a thermite mixture of copper oxide and aluminum powders are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into the 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 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 ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model [1], 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.

  8. 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)

  9. Universal Responses of Cyclic-Oxidation Models Studied

    Science.gov (United States)

    Smialek, James L.

    2003-01-01

    Oxidation is an important degradation process for materials operating in the high-temperature air or oxygen environments typical of jet turbine or rocket engines. Reaction of the combustion gases with the component material forms surface layer scales during these oxidative exposures. Typically, the instantaneous rate of reaction is inversely proportional to the existing scale thickness, giving rise to parabolic kinetics. However, more realistic applications entail periodic startup and shutdown. Some scale spallation may occur upon cooling, resulting in loss of the protective diffusion barrier provided by a fully intact scale. Upon reheating, the component will experience accelerated oxidation due to this spallation. Cyclic-oxidation testing has, therefore, been a mainstay of characterization and performance ranking for high-temperature materials. Models simulate this process by calculating how a scale spalls upon cooling and regrows upon heating (refs. 1 to 3). Recently released NASA software (COSP for Windows) allows researchers to specify a uniform layer or discrete segments of spallation (ref. 4). Families of model curves exhibit consistent regularity and trends with input parameters, and characteristic features have been empirically described in terms of these parameters. Although much insight has been gained from experimental and model curves, no equation has been derived that can describe this behavior explicitly as functions of the key oxidation parameters.

  10. 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.

  11. 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

  12. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    Science.gov (United States)

    Supercritical Water Oxidation (SCWO) evaluated for five compounds: acetic acid, 2,4-dichlorophenol, pentachlorophenol, pyridine, 2,4-dichlorophenoxyacetic acid (methyl ester). inetic models were developed for acetic acid, 2,4-dichlorophenol, and pyridine. he test compounds were e...

  13. 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…

  14. Structure and properties of molybdenum oxide nitrides as model systems for selective oxidation catalysts

    Directory of Open Access Journals (Sweden)

    Lerch Martin

    2011-07-01

    Full Text Available Abstract Molybdenum oxide nitride (denoted as Mo(O,N3 was obtained by ammonolysis of α-MoO3 with gaseous ammonia. Electronic and geometric structure, reducibility, and conductivity of Mo(O,N3 were investigated by XRD, XAS, UV-Vis spectroscopy, and impedance measurements. Catalytic performance in selective propene oxidation was determined by online mass spectrometry und gas chromatography. Upon incorporation of nitrogen, Mo(O,N3 maintained the characteristic layer structure of α-MoO3. XRD analysis showed an increased structural disorder in the layers while nitrogen is removed from the lattice of Mo(O,N3 at temperatures above ~600 K. Compared to regular α-MoO3, Mo(O,N3 exhibited a higher electronic and ionic conductivity and an onset of reduction in propene at lower temperatures. Surprisingly, α-MoO3 and Mo(O,N3 exhibited no detectable differences in onset temperatures of propene oxidation and catalytic selectivity or activity. Apparently, the increased reducibility, oxygen mobility, and conductivity of Mo(O,N3 compared to α-MoO3 had no effect on the catalytic behavior of the two catalysts. The results presented confirm the suitability of molybdenum oxide nitrides as model systems for studying bulk contributions to selective oxidation.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-09-01

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

  16. 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.

  17. 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.

  18. 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...... methods which advantageously minimize the number of modeling parameters and the parameters used have direct physicochemical meaning. This is accomplished by (i) employing an improved cell model where the representative 0-D resistive-capacitive type EC elements are replaced by analytical 1-D porous......) constraining the parameter values during fitting to ranges of physically reasonable values. Using these methods, the number of fitting parameters for four impedance spectra measured with isolated changes to the fuel and oxidant gas compositions, has been reduced from 80 to 21-34 depending on the model...

  19. 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

  20. 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

  1. 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

  2. A microkinetic model of the methanol oxidation over silver

    DEFF Research Database (Denmark)

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

    2003-01-01

    , respectively. The model explains observed reaction orders, selectivity, apparent activation enthalpies and the choice of industrial reaction conditions. More interesting the model disproves the notion that the mechanism deduced from surface science in UHV cannot be responsible for formaldehyde synthesis......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...

  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. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

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

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

  6. 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 hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

  8. 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.

  9. 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.

  10. Modeling of oxidation of structural materials in LBE systems

    Science.gov (United States)

    Steiner, H.; Schroer, C.; Voß, Z.; Wedemeyer, O.; Konys, J.

    2008-02-01

    In recent years, liquid metal alloys have been examined in the light of various applications in technical systems the most famous example is the sodium cooled Fast Breeder Reactor. One major problem in non-isothermal heavy liquid metal systems lies in the corrosion of their structural components. The formation of oxide scales on the structural components is considered as a viable measure in limiting the dissolution rates in the hot parts in lead and lead-bismuth loops. Models for oxide scale growth under the action of flowing liquid metals have been implemented in the newly developed code MATLIM, which allow calculating the evolution of the oxide scales on structural materials in multi-modular loops. There are thermo-hydraulic limitations on oxygen supply from the liquid metal to the structural materials, the oxygen mass transfer coefficient in the liquid metal, which depends on the flow conditions, being rate-determining. This seems to explain, for example, why in the first stage of oxidation of stainless steels slowly growing, dense single layer Fe/Cr spinel scales are formed.

  11. Evaluation of discrepancy between measured and modelled oxidized mercury species

    Directory of Open Access Journals (Sweden)

    G. Kos

    2013-05-01

    Full Text Available L. Zhang et al. (2012, in a recent report, compared model estimates with new observations of oxidized and particulate mercury species (Hg2+ and Hgp in the Great Lakes region and found that the sum of Hg2+ and Hgp varied between a factor of 2 to 10 between measurements and model. They suggested too high emission inputs as Hg2+ and too fast oxidative conversion of Hg0 to Hg2+ and Hgp as possible causes. This study quantitatively explores measurement uncertainties in detail. These include sampling efficiency, composition of sample, interfering species and calibration errors. Model (Global/Regional Atmospheric Heavy Metals Model – GRAHM sensitivity experiments are used to examine the consistency between various Hg measurements and speciation of Hg near emission sources to better understand the discrepancies between modelled and measured concentrations of Hg2+ and Hgp. We find that the ratio of Hg0, Hg2+ and Hgp in the emission inventories, measurements of surface air concentrations of oxidized Hg and measurements of wet deposition are currently inconsistent with each other in the vicinity of emission sources. Current speciation of Hg emissions suggests higher concentrations of Hg2+ in air and in precipitation near emission sources; however, measured air concentrations of Hg2+ and measured concentrations of Hg in precipitation are not found to be significantly elevated near emission sources compared to the remote regions. The averaged unbiased root mean square error (RMSE between simulated and observed concentrations of Hg2+ is found to be reduced by 42% and for Hgp reduced by 40% for 21 North American sites investigated, when a ratio for Hg0 : Hg2+ : Hgp in the emissions is changed from 50 : 40 : 10 (as specified in the original inventories to 90 : 8 : 2. Unbiased RMSE reductions near emissions sources in the eastern United States and Canada are found to be reduced by up to 58% for Hg2+. Significant improvement in the model simulated spatial

  12. Oxidative stress in toxicology: established mammalian and emerging piscine model systems.

    Science.gov (United States)

    Kelly, K A; Havrilla, C M; Brady, T C; Abramo, K H; Levin, E D

    1998-07-01

    Interest in the toxicological aspects of oxidative stress has grown in recent years, and research has become increasingly focused on the mechanistic aspects of oxidative damage and cellular responses in biological systems. Toxic consequences of oxidative stress at the subcellular level include lipid peroxidation and oxidative damage to DNA and proteins. These effects are often used as end points in the study of oxidative stress. Typically, mammalian species have been used as models to study oxidative stress and to elucidate the mechanisms underlying cellular damage and response, largely because of the interest in human health issues surrounding oxidative stress. However, it is becoming apparent that oxidative stress also affects aquatic organisms exposed to environmental pollutants. Research in fish has demonstrated that mammalian and piscine systems exhibit similar toxicological and adaptive responses to oxidative stress. This suggests that piscine models, in addition to traditional mammalian models, may be useful for further understanding the mechanisms underlying the oxidative stress response.

  13. 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.

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

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... have been compared to the experimental results of de Wilde and van Tiggelen (1968) who measured the laminar burning velocities for HOCHO flames over a range of stoichiometries and dilution ratios. The modeling predictions are generally satisfactory. The governing reaction mechanisms are outlined based...... 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...

  15. 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.

  16. Preservation engineering assets developed from an oxidation predictive model

    Directory of Open Access Journals (Sweden)

    Coutelieris Frank A.

    2016-01-01

    Full Text Available A previously developed model which effectively predicts the probability of olive oil reaching the end of its shelf-life within a certain time frame was tested for its response when the convective diffusion of oxygen through packaging material is taken in account. Darcy’s Law was used to correlate the packaging permeability with the oxygen flow through the packaging materials. Mass transport within the food-packaging system was considered transient and the relative one-dimensional differential equations along with appropriate initial and boundary conditions were numerically solved. When the Peclet (Pe number was used to validate the significance of the oxygen transport mechanism through packaging, the model results confirmed the Arrhenius type dependency of diffusion, where the slope of the line per material actually indicated their –Ea/R. Furthermore, Pe could not be correlated to the hexanal produced in samples stored under light. Photo-oxidation has a significant role in the oxidative degradation of olive oil confirmed by the shelf-assessing test. The validity of our model for the oxygen diffusion driven systems, was also confirmed, for that reason the predictive boundaries were set. Results safely indicated the significance of applying a self-assessing process to confirm the packaging selection process for oxygen sensitive food via this model.

  17. 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.

  18. 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.

  19. 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

  20. Lithium ion transport in a model of amorphous polyethylene oxide.

    Energy Technology Data Exchange (ETDEWEB)

    Boinske, P. T.; Curtiss, L.; Halley, J. W.; Lin, B.; Sutjianto, A.; Chemical Engineering; Univ. of Minnesota

    1996-01-01

    We have made a molecular dynamics study of transport of a single lithium ion in a previously reported model of amorphous polyethylene oxide. New ab initio calculations of the interaction of the lithium ion with 1,2-dimethoxyethane and with dimethyl ether are reported which are used to determine force fields for the simulation. We report preliminary calculations of solvation energies and hopping barriers and a calculation of the ionic conductivity which is independent of any assumptions about the mechanism of ion transport. We also report some details of a study of transport of the trapped lithium ion on intermediate time and length scales.

  1. Oxidative stress in toxicology: established mammalian and emerging piscine model systems.

    OpenAIRE

    Kelly, K.A.; Havrilla, C M; Brady, T C; Abramo, K H; Levin, E.D.

    1998-01-01

    Interest in the toxicological aspects of oxidative stress has grown in recent years, and research has become increasingly focused on the mechanistic aspects of oxidative damage and cellular responses in biological systems. Toxic consequences of oxidative stress at the subcellular level include lipid peroxidation and oxidative damage to DNA and proteins. These effects are often used as end points in the study of oxidative stress. Typically, mammalian species have been used as models to study o...

  2. 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.)

  3. Model studies with gold: a versatile oxidation and hydrogenation catalyst.

    Science.gov (United States)

    Pan, Ming; Gong, Jinlong; Dong, Guangbin; Mullins, C Buddie

    2014-03-18

    Historically, scientists have considered gold an inert catalyst constituent. However, in recent decades, chemists have discovered that nanoscale gold shows exceptional activity for many chemical reactions. They have investigated model gold surfaces in order to obtain fundamental understanding of catalytic properties. In this Account, we present our current understanding of oxidation and hydrogenation reactions on the Au(111) single crystal as a planar representative of gold catalysts, revealing the interesting surface chemistry of gold. We begin by comparing two inverse reactions, alcohol oxidation and aldehyde hydrogenation, on a Au(111) surface. Beyond the expected different chemistry, we observe intriguing similarities since the same surface is employed. First, both molecular oxygen and hydrogen have high barriers to dissociation on Au(111), and frequently chemists study reactions here by using atomic O and H to populate the surfaces. Recombinative desorption features of oxygen and hydrogen are apparent at ∼500 and ∼110 K, lower than other transition metals. These results indicate that oxygen and hydrogen have low desorption activation energies and weakly chemisorb on the surface, likely leading to selective reactions. On the oxygen-precovered Au(111) surface, alcohols are selectively oxidized to aldehydes. Similarly, weakly bound hydrogen atoms on Au(111) also show chemoselective reactivity for hydrogenation of propionaldehyde and acetone. The second similarity is that the gold surface activates self-coupling of alcohol or aldehyde with oxygen or hydrogen, resulting in the formation of esters and ethers, respectively, in alcohol oxidation and aldehyde hydrogenation. During these two reactions, both alkoxy groups and alcohol-like species show up as intermediates, which likely play a key role in the formation of coupling products. In addition, the cross coupling reaction between alcohol and aldehyde occurs on both O- and H-modified surfaces, yielding the

  4. 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.

  5. Modeling of sulfur oxide removal in circulating fluidized bed absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Mao, D.; Edwards, J.R.; Kuznetsov, A.V. [North Carolina State Univ., Raleigh, NC (United States). Dept. of Mechanical and Aerospace Engineering; Srivastava, R. [U.S. Environmental Protection Agency, Research Triangle Park, NC (United States). Air Pollution Prevention and Control Division

    2002-07-01

    This paper presents a model to simulate a circulating fluidized bed absorber (CFBA) that combines flow, mixing, and reaction through residence time distribution (RTD). These parameters are often overlooked in existing simulation models. In addition, the paper presents a newly developed gas-solid reaction model for sulphur dioxide removal by limestone. For the reaction model that considers RTD inside the core and annulus regions of CFBA, the macrochemical reaction is simulated according to microchemical reaction dynamics. The proposed model can predict sulphur dioxide and limestone distributions inside the CFBA and calculate how much limestone is needed to remove an appropriate amount of sulphur dioxide. Sulphur dioxide concentration at the outlet of the CFBA decreases as the distance of the CFBA increases from the bottom of the core region. Limestone concentration varies only very slightly in the core region, suggesting that limestone in the CFBA is efficiently utilized to remove sulphur oxide. Sulphur dioxide partial pressure at the exit of the CFBA decreases as fresh limestone increases at the inlet to the CFBA. 16 refs., 8 figs.

  6. 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

  7. 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

  8. 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.

  9. Modelling of diffusion and conductivity relaxation of oxide ceramics

    Science.gov (United States)

    Preis, Wolfgang

    2016-12-01

    A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.

  10. 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.

  11. 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...

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

    Science.gov (United States)

    Zhang, Xueqing; Bieberle-Hütter, Anja

    2016-06-08

    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.

  13. 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

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Modeling of Alkane Oxidation Using Constituents and Species

    Science.gov (United States)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

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

  3. Effects of aerosols on tropospheric oxidants: A global model study

    Science.gov (United States)

    Tie, Xuexi; Brasseur, Guy; Emmons, Louisa; Horowitz, Larry; Kinnison, Douglas

    2001-10-01

    The global distributions of sulfate and soot particles in the atmosphere are calculated, and the effect of aerosol particles on tropospheric oxidants is studied using a global chemical/transport/aerosol model. The model is developed in the framework of the National Center for Atmospheric Research (NCAR) global three-dimensional chemical/transport model (Model for Ozone and Related Chemical Tracers (MOZART)). In addition to the gas-phase photochemistry implemented in the MOZART model, the present study also accounts for the formation of sulfate and black carbon aerosols as well as for heterogeneous reactions on particles. The simulated global sulfate aerosol distributions and seasonal variation are compared with observations. The seasonal variation of sulfate aerosols is in agreement with measurements, except in the Arctic region. The calculated vertical profiles of sulfate aerosol agree well with the observations over North America. In the case of black carbon the calculated surface distribution is in fair agreement with observations. The effects of aerosol formation and heterogeneous reactions on the surface of sulfate aerosols are studied. The model calculations show the following: (1) The concentration of H2O2 is reduced when sulfate aerosols are formed due to the reaction of SO2 + H2O2 in cloud droplets. The gas-phase reaction SO2 + OH converts OH to HO2, but the reduction of OH and enhancement of HO2 are insignificant (<3%). (2) The heterogeneous reaction of HO2 on the surface of sulfate aerosols produces up to 10% reduction of hydroperoxyl radical (HO2) with an uptake coefficient of 0.2. However, this uptake coefficient could be overestimated, and the results should be regard as an upper limit estimation. (3) The N2O5 reaction on the surface of sulfate aerosols leads to an 80% reduction of NOx at middle to high latitudes during winter. Because ozone production efficiency is low in winter, ozone decreases by only 10% as a result of this reaction. However

  4. 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.

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

    Directory of Open Access Journals (Sweden)

    David M. Goldie

    2016-11-01

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

  6. Asparagine decarboxylation by lipid oxidation products in model systems.

    Science.gov (United States)

    Hidalgo, Francisco J; Delgado, Rosa M; Navarro, José L; Zamora, Rosario

    2010-10-13

    The decarboxylation of asparagine in the presence of alkanals, alkenals, and alkadienals, among other lipid derivatives, was studied in an attempt to understand the reaction pathways by which some lipid oxidation products are able to convert asparagine into acrylamide. Asparagine was converted into 3-aminopropionamide in the presence of lipid derivatives as a function of reaction conditions (pH, water content, time, and temperature), as well as the type and amount of lipid compound involved. Alkadienals (and analogous ketodienes) were the most reactive lipids followed by hydroperoxides and alkenals. Saturated carbonyls and polyunsaturated fatty acids, or other polyunsaturated derivatives, also exhibited some reactivity. On the other hand, saturated lipids or monounsaturated alcohols did not degrade asparagine. A mechanism for the decarboxylation of asparagine in the presence of alkadienals based on the deuteration results obtained when asparagine/2,4-decadienal model systems were heated in the presence of deuterated water was proposed. The activation energy (E(a)) of asparagine decarboxylation by 2,4-decadienal was 81.0 kJ/mol, which is higher than that found for the conversion of 3-aminopropionamide into acrylamide in the presence of 2,4-decadienal. This result points to the decarboxylation step as the key step in the conversion of asparagine into acrylamide in the presence of alkadienals. Therefore, any inhibiting strategy for suppressing the formation of acrylamide by alkadienals should be mainly directed to the inhibition of this step.

  7. 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.

  8. 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.

  9. 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

  10. Inhibition of Oxidation in Nuclear Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Phil Winston; James W. Sterbentz; William E. Windes

    2013-10-01

    Graphite is a fundamental material of high temperature gas cooled nuclear reactors, providing both structure and neutron moderation. Its high thermal conductivity, chemical inertness, thermal heat capacity, and high thermal structural stability under normal and off normal conditions contribute to the inherent safety of these reactor designs. One of the primary safety issues for a high temperature graphite reactor core is the possibility of rapid oxidation of the carbon structure during an off normal design basis event where an oxidizing 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 postualed 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°C. The proposed addition of B4C to graphite components in the nuclear core would necessarily be enriched in B-11 isotope in order to minimize 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.

  11. 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

  12. 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.

  13. Model-based evaluation of the role of Anammox on nitric oxide and nitrous oxide productions in membrane aerated biofilm reactor

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Smets, Barth F.; Yuan, Zhiguo;

    2013-01-01

    A multispecies one-dimensional biofilm model considering nitric oxide (NO) and nitrous oxide (N2O) productions for membrane aerated biofilm reactor (MABR) that remove nitrogen autotrophically through aerobic ammonia oxidation followed by Anammox is used to study the role of Anammox activity on th...

  14. 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.

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

    Directory of Open Access Journals (Sweden)

    Gabrielle Benoît

    2006-11-01

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

  16. 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...

  17. 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.

  18. 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.

  19. Oxidative Damage in the Aging Heart: an Experimental Rat Model

    Science.gov (United States)

    Marques, Gustavo Lenci; Neto, Francisco Filipak; Ribeiro, Ciro Alberto de Oliveira; Liebel, Samuel; de Fraga, Rogério; Bueno, Ronaldo da Rocha Loures

    2015-01-01

    Introduction: Several theories have been proposed to explain the cause of ‘aging’; however, the factors that affect this complex process are still poorly understood. Of these theories, the accumulation of oxidative damage over time is among the most accepted. Particularly, the heart is one of the most affected organs by oxidative stress. The current study, therefore, aimed to investigate oxidative stress markers in myocardial tissue of rats at different ages. Methods: Seventy-two rats were distributed into 6 groups of 12 animals each and maintained for 3, 6, 9, 12, 18 and 24 months. After euthanasia, the heart was removed and the levels of non-protein thiols, lipid peroxidation, and protein carbonylation, as well as superoxide dismutase and catalase activities were determined. Results: Superoxide dismutase, catalase activity and lipid peroxidation were reduced in the older groups of animals, when compared with the younger group. However, protein carbonylation showed an increase in the 12-month group followed by a decrease in the older groups. In addition, the levels of non-protein thiols were increased in the 12-month group and not detected in the older groups. Conclusion: Our data showed that oxidative stress is not associated with aging in the heart. However, an increase in non-protein thiols may be an important factor that compensates for the decrease of superoxide dismutase and catalase activity in the oldest rats, to maintain appropriate antioxidant defenses against oxidative insults. PMID:27006709

  20. In vitro model suggests oxidative stress involved in keratoconus disease

    Science.gov (United States)

    Karamichos, D.; Hutcheon, A. E. K.; Rich, C. B.; Trinkaus-Randall, V.; Asara, J. M.; Zieske, J. D.

    2014-04-01

    Keratoconus (KC) affects 1:2000 people and is a disorder where cornea thins and assumes a conical shape. Advanced KC requires surgery to maintain vision. The role of oxidative stress in KC remains unclear. We aimed to identify oxidative stress levels between human corneal keratocytes (HCKs), fibroblasts (HCFs) and keratoconus cells (HKCs). Cells were cultured in 2D and 3D systems. Vitamin C (VitC) and TGF-β3 (T3) were used for 4 weeks to stimulate self-assembled extracellular matrix (ECM). No T3 used as controls. Samples were analyzed using qRT-PCR and metabolomics. qRT-PCR data showed low levels of collagen I and V, as well as keratocan for HKCs, indicating differentiation to a myofibroblast phenotype. Collagen type III, a marker for fibrosis, was up regulated in HKCs. We robustly detected more than 150 metabolites of the targeted 250 by LC-MS/MS per condition and among those metabolites several were related to oxidative stress. Lactate levels, lactate/malate and lactate/pyruvate ratios were elevated in HKCs, while arginine and glutathione/oxidized glutathione ratio were reduced. Similar patterns found in both 2D and 3D. Our data shows that fibroblasts exhibit enhanced oxidative stress compared to keratocytes. Furthermore the HKC cells exhibit the greatest level suggesting they may have a myofibroblast phenotype.

  1. Phenolic mediators enhance the manganese peroxidase catalyzed oxidation of recalcitrant lignin model compounds and synthetic lignin.

    Science.gov (United States)

    Nousiainen, Paula; Kontro, Jussi; Manner, Helmiina; Hatakka, Annele; Sipilä, Jussi

    2014-11-01

    Fungal oxidative enzymes, such as peroxidases and laccases, are the key catalysts in lignin biodegradation in vivo, and consequently provide an important source for industrial ligninolytic biocatalysts. Recently, it has been shown that some syringyl-type phenolics have potential as industrial co-oxidants or mediators, in laccase-catalyzed modification of lignocellulosic material. We have now studied the effect of such mediators with ligninolytic peroxidases on oxidation of the most recalcitrant lignin model compounds. We found that they are able to enhance the manganese peroxidase (MnP) catalyzed oxidation reactions of small non-phenolic compounds, veratryl alcohol and veratrylglycerol β-guaiacyl ether (adlerol), which are not usually oxidized by manganese peroxidases alone. In these experiments we compared two peroxidases from white-rot fungi, MnP from Phlebia sp. Nf b19 and versatile peroxidase (VP) from Bjerkandera adusta under two oxidation conditions: (i) the Mn(III) initiated mediated oxidation by syringyl compounds and (ii) the system involving MnP-dependent lipid peroxidation, both with production of (hydrogen) peroxides in situ to maintain the peroxidase catalytic cycle. It was found that both peroxidases produced α-carbonyl oxidation product of veratryl alcohol in clearly higher yields in reactions mediated by phenoxy radicals than in lipid-peroxyl radical system. The oxidation of adlerol, on the other hand, was more efficient in lipid-peroxidation-system. VP was more efficient than MnP in the oxidation of veratryl alcohol and showed its lignin peroxidase type activity in the reaction conditions indicated by some cleavage of Cα-Cβ-bond of adlerol. Finally, the mediator assisted oxidation conditions were applied in the oxidation of synthetic lignin (DHP) and the structural analysis of the oxidized polymers showed clear modifications in the polymer outcome, e.g. the oxidation resulted in reduced amount of aliphatic hydroxyls indicated by (31)P NMR.

  2. 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.

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

    Directory of Open Access Journals (Sweden)

    Jiali Ying

    2015-10-01

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

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

    Science.gov (United States)

    Cui, Yanshan; Weng, Liping

    2013-07-02

    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.

  5. Activity Calculation by Application of Sub-Regular Solution Model in Binary Oxide Systems

    Institute of Scientific and Technical Information of China (English)

    HOU Yan-qing; XIE Gang; TAO Dong-ping; LI Rong-xing; YU Xiao-hua

    2012-01-01

    To confirm sub-regular solution model valid for predicting the activity of component in binary oxide systems, seven systems in the whole concentration and twelve systems presenting saturation concentration have been studied. The total average relative errors of component 1 and 2 are 3.2 % and 4.1% respectively by application of the sub-regular solution model into the systems within the whole concentration. However, the total average relative errors are 16 % and 1088 % in the systems presenting saturation concentration. The results show that sub-regular solu- tion model is not good for predicting the systems presenting saturation concentration, especially for the systems con- taining acidic or neutral oxide. The reason may be that the influence of the two types of oxide on the configuration is greater in binary oxide systems. These oxides can be present in the form of complex anion partly, Si-O, Al-O, Ti-O and so on, for example (SiO4)4-. That is contrary to sub-regular solution model which is supposed that the oxide systems consist of cation and O2-. But compared with regular solution model and quasi-regular solution model, sub- regular solution model is closer to the characteristics of actual solution and the calculated results are superior.

  6. 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...

  7. 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...

  8. 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.

  9. Temperature Dependent Residual Stress Models for Ultra-High-Temperature Ceramics on High Temperature Oxidation

    Science.gov (United States)

    Wang, Ruzhuan; Li, Weiguo

    2016-11-01

    The strength of SiC-depleted layer of ultra-high-temperature ceramics on high temperature oxidation degrades seriously. The research for residual stresses developed within the SiC-depleted layer is important and necessary. In this work, the residual stress evolutions in the SiC-depleted layer and the unoxidized substrate in various stages of oxidation are studied by using the characterization models. The temperature and oxidation time dependent mechanical/thermal properties of each phase in SiC-depleted layer are considered in the models. The study shows that the SiC-depleted layer would suffer from large tensile stresses due to the great temperature changes and the formation of pores on high temperature oxidation. The stresses may lead to the cracking and even the delamination of the oxidation layer.

  10. 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.

  11. 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.

  12. Optimization of a new flow design for solid oxide cells using computational fluid dynamics modelling

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig;

    2016-01-01

    Design of a gas distributor to distribute gas flow into parallel channels for Solid Oxide Cells (SOC) is optimized, with respect to flow distribution, using Computational Fluid Dynamics (CFD) modelling. The CFD model is based on a 3d geometric model and the optimized structural parameters include...

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Detailed Multi-dimensional Modeling of Direct Internal Reforming Solid Oxide Fuel Cells.

    Science.gov (United States)

    Tseronis, K; Fragkopoulos, I S; Bonis, I; Theodoropoulos, C

    2016-06-01

    Fuel flexibility is a significant advantage of solid oxide fuel cells (SOFCs) and can be attributed to their high operating temperature. Here we consider a direct internal reforming solid oxide fuel cell setup in which a separate fuel reformer is not required. We construct a multidimensional, detailed model of a planar solid oxide fuel cell, where mass transport in the fuel channel is modeled using the Stefan-Maxwell model, whereas the mass transport within the porous electrodes is simulated using the Dusty-Gas model. The resulting highly nonlinear model is built into COMSOL Multiphysics, a commercial computational fluid dynamics software, and is validated against experimental data from the literature. A number of parametric studies is performed to obtain insights on the direct internal reforming solid oxide fuel cell system behavior and efficiency, to aid the design procedure. It is shown that internal reforming results in temperature drop close to the inlet and that the direct internal reforming solid oxide fuel cell performance can be enhanced by increasing the operating temperature. It is also observed that decreases in the inlet temperature result in smoother temperature profiles and in the formation of reduced thermal gradients. Furthermore, the direct internal reforming solid oxide fuel cell performance was found to be affected by the thickness of the electrochemically-active anode catalyst layer, although not always substantially, due to the counter-balancing behavior of the activation and ohmic overpotentials.

  19. 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

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

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-06-01

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

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

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-08-01

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

  2. Modelling of composition and phase changes in multiphase alloys due to growth of an oxide layer

    Energy Technology Data Exchange (ETDEWEB)

    Nijdam, T.J. [Materials Innovation Institute (M2i) and Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft (Netherlands); Sloof, W.G. [Materials Innovation Institute (M2i) and Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft (Netherlands)], E-mail: w.g.sloof@tudelft.nl

    2008-10-15

    A coupled thermodynamic-kinetic oxidation model is presented for the selective, external oxidation of the most reactive alloy constituent of a multicomponent multiphase alloy. The model computes the composition depth profiles of the alloy constituents in the alloy as well as the evolution in the phase fractions in the alloy as function of oxidation time. The applicability of the model is illustrated through several examples. For the isothermal and cyclic oxidation of single- and two-phase binary alloys excellent agreement was obtained between the numerical calculations and the corresponding analytical solutions. For the isothermal oxidation of two {gamma}+{beta} NiCrAl alloys with different initial volume fractions of the {beta} phase, very good agreement was obtained between experimentally and calculated composition depth profiles. Finally, the effect of alloying additions on the phase evolution in the alloy was studied for the isothermal oxidation of freestanding MCrAlY (M = Ni, Co) coatings. It is shown that for a similar bulk Al and Cr content in the coating, the concentration profiles of Al in the coating after oxidation can be significantly affected by alloying with elements like Co, Ta and Re. Consequently, the multicomponent and multiphase character of the MCrAlY coating has to be taken into account when performing lifetime studies.

  3. 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

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

    Directory of Open Access Journals (Sweden)

    Xiaoyan Ding

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

  5. 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.

  6. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

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

    2002-01-01

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

  7. 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...... dynamics during both nitrification and denitrification in biological N removal. Six additional processes and three additional reactants, all involved in known biochemical reactions, have been added. The validity and applicability of the model is demonstrated by comparing simulations with experimental data...... on N2O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO2– participates as final electron acceptor compared to the oxic pathway. Among...

  8. Configurational Model for Conductivity of Stabilized Fluorite Structure Oxides

    DEFF Research Database (Denmark)

    Poulsen, Finn Willy

    1981-01-01

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

  9. Effect of metal chelators on the oxidative stability of model wine.

    Science.gov (United States)

    Kreitman, Gal Y; Cantu, Annegret; Waterhouse, Andrew L; Elias, Ryan J

    2013-10-02

    Oxidation is a major problem with respect to wine quality, and winemakers have few tools at their disposal to control it. In this study, the effect of exogenous Fe(II) (bipyridine; Ferrozine) and Fe(III) chelators (ethylenediaminetetraacetic acid, EDTA; phytic acid) on nonenzymatic wine oxidation was examined. The ability of these chelators to affect the formation of 1-hydroxyethyl radicals (1-HER) and acetaldehyde was measured using a spin trapping technique with electron paramagnetic resonance (EPR) and by HPLC-PDA, respectively. The chelators were then investigated for their ability to prevent the oxidative loss of an important aroma-active thiol, 3-mercaptohexan-1-ol (3MH). The Fe(II)-specific chelators were more effective than the Fe(III) chelators with respect to 1-HER inhibition during the early stages of oxidation and significantly reduced oxidation markers compared to a control during the study. However, although the addition of Fe(III) chelators was less effective or even showed an initial pro-oxidant activity, the Fe(III) chelators proved to be more effective antioxidants compared to Fe(II) chelators after 8 days of accelerated oxidation. In addition, it is shown for the first time that Fe(II) and Fe(III) chelators can significantly inhibit the oxidative loss of 3MH in model wine.

  10. 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.

  11. 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.

  12. 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

    was varied from very oxidizing to strongly reducing conditions. The results supplement high-pressure data from RCM (900–1100 K) and shock tubes (900–2200 K). At the reducing conditions ( U = 12), oxidation started at 748–775 K while it was shifted to 798–823 K for stoichiometric and oxidizing conditions ( U......, 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...

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Validation of membrane protein topology models by oxidative labeling and mass spectrometry.

    Science.gov (United States)

    Pan, Yan; Ruan, Xiang; Valvano, Miguel A; Konermann, Lars

    2012-05-01

    Computer-assisted topology predictions are widely used to build low-resolution structural models of integral membrane proteins (IMPs). Experimental validation of these models by traditional methods is labor intensive and requires modifications that might alter the IMP native conformation. This work employs oxidative labeling coupled with mass spectrometry (MS) as a validation tool for computer-generated topology models. ·OH exposure introduces oxidative modifications in solvent-accessible regions, whereas buried segments (e.g., transmembrane helices) are non-oxidizable. The Escherichia coli protein WaaL (O-antigen ligase) is predicted to have 12 transmembrane helices and a large extramembrane domain (Pérez et al., Mol. Microbiol. 2008, 70, 1424). Tryptic digestion and LC-MS/MS were used to map the oxidative labeling behavior of WaaL. Met and Cys exhibit high intrinsic reactivities with ·OH, making them sensitive probes for solvent accessibility assays. Overall, the oxidation pattern of these residues is consistent with the originally proposed WaaL topology. One residue (M151), however, undergoes partial oxidation despite being predicted to reside within a transmembrane helix. Using an improved computer algorithm, a slightly modified topology model was generated that places M151 closer to the membrane interface. On the basis of the labeling data, it is concluded that the refined model more accurately reflects the actual topology of WaaL. We propose that the combination of oxidative labeling and MS represents a useful strategy for assessing the accuracy of IMP topology predictions, supplementing data obtained in traditional biochemical assays. In the future, it might be possible to incorporate oxidative labeling data directly as constraints in topology prediction algorithms.

  2. 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

  3. 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.

  4. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    Science.gov (United States)

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  5. 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.

  6. A Functional Group Oxidation Model (FGOM for SOA formation and aging

    Directory of Open Access Journals (Sweden)

    X. Zhang

    2012-12-01

    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. (2012 is discussed.

  7. 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.

  8. Integrative Model of Oxidative Stress Adaptation in the Fungal Pathogen Candida albicans.

    Directory of Open Access Journals (Sweden)

    Chandrasekaran Komalapriya

    Full Text Available The major fungal pathogen of humans, Candida albicans, mounts robust responses to oxidative stress that are critical for its virulence. These responses counteract the reactive oxygen species (ROS that are generated by host immune cells in an attempt to kill the invading fungus. Knowledge of the dynamical processes that instigate C. albicans oxidative stress responses is required for a proper understanding of fungus-host interactions. Therefore, we have adopted an interdisciplinary approach to explore the dynamical responses of C. albicans to hydrogen peroxide (H2O2. Our deterministic mathematical model integrates two major oxidative stress signalling pathways (Cap1 and Hog1 pathways with the three major antioxidant systems (catalase, glutathione and thioredoxin systems and the pentose phosphate pathway, which provides reducing equivalents required for oxidative stress adaptation. The model encapsulates existing knowledge of these systems with new genomic, proteomic, transcriptomic, molecular and cellular datasets. Our integrative approach predicts the existence of alternative states for the key regulators Cap1 and Hog1, thereby suggesting novel regulatory behaviours during oxidative stress. The model reproduces both existing and new experimental observations under a variety of scenarios. Time- and dose-dependent predictions of the oxidative stress responses for both wild type and mutant cells have highlighted the different temporal contributions of the various antioxidant systems during oxidative stress adaptation, indicating that catalase plays a critical role immediately following stress imposition. This is the first model to encapsulate the dynamics of the transcriptional response alongside the redox kinetics of the major antioxidant systems during H2O2 stress in C. albicans.

  9. Integrative Model of Oxidative Stress Adaptation in the Fungal Pathogen Candida albicans.

    Science.gov (United States)

    Komalapriya, Chandrasekaran; Kaloriti, Despoina; Tillmann, Anna T; Yin, Zhikang; Herrero-de-Dios, Carmen; Jacobsen, Mette D; Belmonte, Rodrigo C; Cameron, Gary; Haynes, Ken; Grebogi, Celso; de Moura, Alessandro P S; Gow, Neil A R; Thiel, Marco; Quinn, Janet; Brown, Alistair J P; Romano, M Carmen

    2015-01-01

    The major fungal pathogen of humans, Candida albicans, mounts robust responses to oxidative stress that are critical for its virulence. These responses counteract the reactive oxygen species (ROS) that are generated by host immune cells in an attempt to kill the invading fungus. Knowledge of the dynamical processes that instigate C. albicans oxidative stress responses is required for a proper understanding of fungus-host interactions. Therefore, we have adopted an interdisciplinary approach to explore the dynamical responses of C. albicans to hydrogen peroxide (H2O2). Our deterministic mathematical model integrates two major oxidative stress signalling pathways (Cap1 and Hog1 pathways) with the three major antioxidant systems (catalase, glutathione and thioredoxin systems) and the pentose phosphate pathway, which provides reducing equivalents required for oxidative stress adaptation. The model encapsulates existing knowledge of these systems with new genomic, proteomic, transcriptomic, molecular and cellular datasets. Our integrative approach predicts the existence of alternative states for the key regulators Cap1 and Hog1, thereby suggesting novel regulatory behaviours during oxidative stress. The model reproduces both existing and new experimental observations under a variety of scenarios. Time- and dose-dependent predictions of the oxidative stress responses for both wild type and mutant cells have highlighted the different temporal contributions of the various antioxidant systems during oxidative stress adaptation, indicating that catalase plays a critical role immediately following stress imposition. This is the first model to encapsulate the dynamics of the transcriptional response alongside the redox kinetics of the major antioxidant systems during H2O2 stress in C. albicans.

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

    Science.gov (United States)

    Karahan, Aydın; Buongiorno, Jacopo

    2010-01-01

    An engineering code to model the irradiation behavior of UO2-PuO2 mixed oxide fuel pins in sodium-cooled fast reactors was developed. The code was named fuel engineering and structural analysis tool (FEAST-OXIDE). FEAST-OXIDE has several modules working in coupled form with an explicit numerical algorithm. These modules describe: (1) fission gas release and swelling, (2) fuel chemistry and restructuring, (3) temperature distribution, (4) fuel-clad chemical interaction and (5) fuel-clad mechanical analysis. Given the fuel pin geometry, composition and irradiation history, FEAST-OXIDE can analyze fuel and cladding thermo-mechanical behavior at both steady-state and design-basis transient scenarios. The code was written in FORTRAN-90 program language. The mechanical analysis module implements the LIFE algorithm. Fission gas release and swelling behavior is described by the OGRES and NEFIG models. However, the original OGRES model has been extended to include the effects of joint oxide gain (JOG) formation on fission gas release and swelling. A detailed fuel chemistry model has been included to describe the cesium radial migration and JOG formation, oxygen and plutonium radial distribution and the axial migration of cesium. The fuel restructuring model includes the effects of as-fabricated porosity migration, irradiation-induced fuel densification, grain growth, hot pressing and fuel cracking and relocation. Finally, a kinetics model is included to predict the clad wastage formation. FEAST-OXIDE predictions have been compared to the available FFTF, EBR-II and JOYO databases, as well as the LIFE-4 code predictions. The agreement was found to be satisfactory for steady-state and slow-ramp over-power accidents.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Radiolytic modelling of spent fuel oxidative dissolution mechanism. Development of the model and testing with experimental data

    Energy Technology Data Exchange (ETDEWEB)

    Merino, J.; Cera, E.; Bruno, J. [ENVIROS, Passeig de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain); Casas, I.; Clarens, F.; Gimenez, J.; de Pablo, J.; Rovira, M. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, ETSEIB, Diagonal 647 H-4, 08028, Barcelona (Spain); Quinones, J. [Ciemat, Av. Complutense 22, 28040 Madrid (Spain); Martinez-Esparza, A. [Enresa, C/ Emilio Vargas 7, 28043 Madrid (Spain)

    2005-07-01

    Full text of publication follows: Assessing the performance of spent nuclear fuel in a potential future geological disposal system requires the understanding and quantification of the important time-dependent phenomena influencing its behaviour on a time-scale up to millions of years. In this work we present the development and testing of a matrix alteration model using recently obtained experimental data. The conceptual model assumes that water will enter in contact with the fuel surface, and then the first process we may expect is the radiolysis of water. Water radiolysis will generate reductants and oxidants and we may expect local oxidising conditions. Because of these local conditions, the surface of the fuel will oxidize. The oxidation of the matrix and the attachment of aqueous ligands able to form strong complexes with its major component will favour the dissolution of the matrix. The oxygen mediated oxidation of the UO{sub 2} matrix is a surface oxidation via a mechanism of electron transfer with the oxygen molecule adsorbed onto the surface of the matrix. Hydrogen peroxide oxidation occurs by radical formation with very high oxidation potentials, and with the radical hydroxyl (.OH) as one of the main species generated in this process. On the other hand, the bicarbonate may act as scavenger of the .OH to form the radical .CO{sub 3}{sup -}. The dissolution processes once the surface sites are oxidised are based on two dissolution steps: surface co-ordination of U(VI) by the aqueous ligands (H{sup +}, H{sub 2}O or HCO{sub 3}{sup -}), and detachment (dissolution) of the product species. All the above processes have been included in the mathematical model and their kinetic constants calibrated with unirradiated UO{sub 2} leaching experiments. Furthermore, testing of the model has been carried out by applying it to a range of leaching experiments available in the framework of the European SFS (Spent Fuel Stability) project. These experiments include both static

  16. Spectroscopic and catalytic investigations of VxOy/SBA-15 and magnesium vanadate model catalysts for selective propene oxidation

    OpenAIRE

    Walter, Anke

    2011-01-01

    The objective of the present work was elucidating structure-activity relationships concerning the individual role of vanadium sites in selective propene oxidation. Two suitable vanadium oxide model catalyst systems were employed: vanadium oxides supported on SBA-15, “VxOy/SBA-15”, and various magnesium vanadate phases. Detailed investigations on the preparation, thermal stability, structure, and structural evolution under reducing and propene oxidizing condition were conducted. Various in sit...

  17. 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.

  18. 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.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  20. 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.

  1. 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.

  2. 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...

  3. Analysis of Residual Performance of UD-CMC in Oxidation Atmosphere Based on a Notch-like Oxidation Model

    Science.gov (United States)

    Sun, Zhigang; Shao, Hongyan; Chen, Xihui; Song, Yingdong

    2016-10-01

    Experimental observation indicates unidirectional ceramic matrix composites (UD-CMC) will react with oxygen under high-temperature atmosphere inhomogeneous. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. Stress concentration near by the fiber notch causes a decline of the mechanic performance of UD-CMC. In this paper, the change rule of fiber notch depth is fitted by circular function. Based on this formula the residual strength and modulus of UD-CMC under 400-900 °C atmosphere are derived. The mechanical performance of unidirectional C/SiC composite is simulated by finite element method. The stress distribution of fiber, matrix and interface are obtained. The residual properties of unidirectional C/SiC composite are predicted by theoretical method and finite element method. And the predicting results are compared with the experiment data. The predicting results show a good accordance with experiment data, which means the notch-like oxidation model can analyze the mechanic performance of UD-CMC efficiently.

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

    Science.gov (United States)

    2008-11-14

    Unlimited 18. NUMBER OF PAGES 15 19a. NAME OF RESPONSIBLE PERSON Martin P. Harmer 19b. TELEPHONE NUMBER (Include area code) 610-758-4227 Standard...American Ceramic Society, 1993. 76(11): p. 2801-8. 26. Dillon, S.J., Tang, M., Carter, W.C., and M.P. Harmer , Complexion: A New Concept for Kinetic...Engineering in Materials Science. Acta Materialia, 2007. 55: p. 6208-18. 27. Dillon, S.J. and M.P. Harmer , Multiple Grain boundary transitions in Ceramics

  5. 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,…).

  6. 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.

  7. 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 \

  8. 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.

  9. 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...

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

    DEFF Research Database (Denmark)

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

    2017-01-01

    A 1-dimensional model of a cathode has been developed in order to understand and predict the performance of cathodes prepared by infiltration of La0.6Sr0.4Co1.05O3-δ (LSC) into porous backbones of Ce0.9Gd0.1O1.95 (CGO). The model accounts for the mixed ionic and electronic conductivity of LSC......, ionic conductivity of CGO, gas transport in the porous cathode, and the oxygen reduction reaction at the surface of percolated LSC. Geometrical variations are applied to reflect a changing microstructure of LSC under varying firing temperatures. Using microstructural parameters obtained from detailed...... parameter variations are presented and discussed with the aim of presenting specific guidelines for optimizing the microstructure of cathodes prepared by infiltration....

  11. 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.

  12. Extending the models for iron and sulfur oxidation in the extreme Acidophile Acidithiobacillus ferrooxidans

    Directory of Open Access Journals (Sweden)

    Holmes David S

    2009-08-01

    Full Text Available Abstract Background Acidithiobacillus ferrooxidans gains energy from the oxidation of ferrous iron and various reduced inorganic sulfur compounds at very acidic pH. Although an initial model for the electron pathways involved in iron oxidation has been developed, much less is known about the sulfur oxidation in this microorganism. In addition, what has been reported for both iron and sulfur oxidation has been derived from different A. ferrooxidans strains, some of which have not been phylogenetically characterized and some have been shown to be mixed cultures. It is necessary to provide models of iron and sulfur oxidation pathways within one strain of A. ferrooxidans in order to comprehend the full metabolic potential of the pangenome of the genus. Results Bioinformatic-based metabolic reconstruction supported by microarray transcript profiling and quantitative RT-PCR analysis predicts the involvement of a number of novel genes involved in iron and sulfur oxidation in A. ferrooxidans ATCC23270. These include for iron oxidation: cup (copper oxidase-like, ctaABT (heme biogenesis and insertion, nuoI and nuoK (NADH complex subunits, sdrA1 (a NADH complex accessory protein and atpB and atpE (ATP synthetase F0 subunits. The following new genes are predicted to be involved in reduced inorganic sulfur compounds oxidation: a gene cluster (rhd, tusA, dsrE, hdrC, hdrB, hdrA, orf2, hdrC, hdrB encoding three sulfurtransferases and a heterodisulfide reductase complex, sat potentially encoding an ATP sulfurylase and sdrA2 (an accessory NADH complex subunit. Two different regulatory components are predicted to be involved in the regulation of alternate electron transfer pathways: 1 a gene cluster (ctaRUS that contains a predicted iron responsive regulator of the Rrf2 family that is hypothesized to regulate cytochrome aa3 oxidase biogenesis and 2 a two component sensor-regulator of the RegB-RegA family that may respond to the redox state of the quinone pool

  13. Trimetazidine prevents oxidative changes induced in a rat model of sporadic type of Alzheimer's disease.

    Directory of Open Access Journals (Sweden)

    Gholamreza Hassanzadeh

    2015-01-01

    Full Text Available Oxidative stress plays a major role in the pathogenesis of Alzheimer's disease (AD of sporadic origin. The expression of DHCR24 (Seladin-1, marker for neuronal oxidative stress and degeneration, has been reported to be altered in the brains of AD patients. In the present study, we investigated the effect of trimetazidine (TMZ on the hippocampal oxidative parameters and the expression of DHCR24 (Seladin-1 in an animal model of sporadic AD. Male rats were pre-treated with TMZ (25 mg/kg after which injected with intracerebroventricular-streptozotocin (ICV-STZ/Saline. Following 2, 7 and 14 days, animals of different groups were sacrificed with their brain excised to detect the hippocampal lipid peroxidation, superoxide dismutase (SOD, catalase activity, DHCR24 (Seladin-1 expression and possible histopathological changes. ICV-STZ administration induced significant oxidative changes in the hippocampus. Meanwhile, TMZ pre-treatment showed to ameliorate the oxidative stress, which was demonstrated by a significant rise in the hippocampal SOD and catalase activity, as well as a significant decrease in the malondialdehyde (MDA level. TMZ administration also increased the expression of DHCR24 (Seladin-1 gene in the hippocampus. In conclusion, our findings indicated a neuroprotective effect of TMZ possibly related to its antioxidant activity resulting in the up-regulation of DHCR24 (Seladin-1. Such TMZ effects may be beneficial in minimizing oxidative stress in sporadic Alzheimer's disease and possible prevention of disease progression.

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

    Science.gov (United States)

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

    2016-12-01

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

  15. 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

  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

    the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

  17. 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

  18. 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--> ...

  19. 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.

  20. Quantitative analysis of anaerobic oxidation of methane (AOM) in marine sediments: a modeling perspective

    NARCIS (Netherlands)

    Regnier, P.; Dale, A.W.; Arndt, S.; LaRowe, D.E.; Mogollon, J.M.; Van Cappellen, P.

    2011-01-01

    Recent developments in the quantitativemodeling of methane dynamics and anaerobic oxidation of methane (AOM) in marine sediments are critically reviewed. The first part of the review begins with a comparison of alternative kinetic models for AOM. The roles of bioenergetic limitations, intermediate c

  1. Aluminum/Copper Oxide/Copper Memristive Devices: Fabrication, Characterization, and Modeling

    Science.gov (United States)

    McDonald, Nathan R.

    Memristive devices have become very popular in recent years due to their potential to dramatically alter logic processing in CMOS circuitry. Memristive devices function as electrical potentiometers, allowing for such diverse applications as memory storage, multi-state logic, and reconfigurable logic gates. This research covered the fabrication, characterization, and modeling of Al/CuxO/Cu memristive devices created by depositing Al top electrodes atop a CuxO film grown using plasma oxidation to grow the oxide on a Cu wafer. Power settings of the plasma oxidation system were shown to control the grown oxide thickness and oxygen concentration, which subsequently affected memristive device behaviors. These memristive devices demonstrated complete nonpolar behavior and could be switched either in a vertical (Al/Cu xO/Cu) or lateral (Al/CuxO/Cu/CuxO/Al) manner. The switching mechanism of these devices was shown to be filamentary in nature. Physical and empirical models of these devices were created for MATLAB, HSPICE, & Verilog A environments. While the physical model proved of limited practical consequence, the robust empirical model allows for rapid prototyping of CMOS-memristor circuitry.

  2. 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.

  3. 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.

  4. 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

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

    Science.gov (United States)

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

    2011-09-15

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

  6. Single catalytic site model for the oxidation of ferrocytochrome c by mitochondrial cytochrome c oxidase.

    OpenAIRE

    Speck, S.H.; Dye, D.; Margoliash, E

    1984-01-01

    A single catalytic site model is proposed to account for the multiphasic kinetics of oxidation of ferrocytochrome c by cytochrome c oxidase (ferrocytochrome c:oxygen oxidoreductase, EC 1.9.3.1). This model involves nonproductive binding of substrate to sites near the catalytic site on cytochrome c oxidase for cytochrome c, decreasing the binding constant for cytochrome c at the catalytic site. This substrate inhibition results in an increase in the first-order rate constant for the dissociati...

  7. Modeling of Proton-Conducting Solid Oxide Fuel Cells Fueled with Syngas

    OpenAIRE

    2014-01-01

    Solid oxide fuel cells (SOFCs) with proton conducting electrolyte (H-SOFCs) are promising power sources for stationary applications. Compared with other types of fuel cells, one distinct feature of SOFC is their fuel flexibility. In this study, a 2D model is developed to investigate the transport and reaction in an H-SOFC fueled with syngas, which can be produced from conventional natural gas or renewable biomass. The model fully considers the fluid flow, mass transfer, heat transfer and r...

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

    Directory of Open Access Journals (Sweden)

    Patricia P. Jumbo-Lucioni

    2013-01-01

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

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

    Science.gov (United States)

    Jumbo-Lucioni, Patricia P; Hopson, Marquise L; Hang, Darwin; Liang, Yongliang; Jones, Dean P; Fridovich-Keil, Judith L

    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

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

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

    Science.gov (United States)

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

    2005-08-01

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

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

    Science.gov (United States)

    Li, Ru; Huang, Jiqing; Kast, Juergen

    2015-05-01

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

  17. 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.

  18. 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.

  19. Modeling anti-Trypanosoma cruzi activity of N-oxide containing heterocycles.

    Science.gov (United States)

    Boiani, Mariana; Cerecetto, Hugo; Gonzalez, Mercedes; Gasteiger, Johann

    2008-01-01

    In the present study a systematic approach was used to model the anti-T. cruzi activity of a series of N-oxide containing heterocycles belonging to four chemical families with a wide structural diversity. The proposed mode of action implies the reduction of the N-oxide moiety; however, the biochemical mechanism underlying the anti-T. cruzi activity is still unkown. For structural representation two types of descriptors were analyzed: quantum chemical (AM1) global descriptors and properties coded by radial distribution function (RDF). Both types of descriptors point to the relevance of electronic properties. The local-RDF (LRDF) identified an electrophilic center at 4.1-4.9 A from the oxygen atom of the N-oxide moiety, although other properties are required to explain the biological activity. While the mode of action of N-oxide containing heterocycles is still unknown, the results obtained here strengthen the importance of the electrophilic character of the molecule and the possible participation of the heterocycle in a reduction process. The ability of these descriptors to distinguish among activity classes was assessed using Kohonen neural networks, and the best clustering descriptors were later used for model building. Different learning algorithms were used for model development, and stratified 10-fold cross-validation was used to evaluate the performance of each classifier. The best results were obtained using k-nearest neighbors (k-NN) and decision tree (J48) methods combined with global descriptors. Since tree-based methods are easily translated into classification rules, the J48 model is a useful tool in the de novo construction of new N-oxide containing heterocycle lead structures.

  20. 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.

  1. 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.

  2. Structural phase diagrams of supported oxide nanowires from extended Frenkel-Kontorova models of diatomic chains.

    Science.gov (United States)

    Noguera, C; Goniakowski, J

    2013-08-28

    Relying on Frenkel Kontorova (FK) models of diatomic chains of increasing levels of complexity, this study presents an overall view of the diversity of structural effects that a compound (oxide) chain supported on a metal may display and helps assigning them to precise microscopic mechanisms. At each stage, the models are solved numerically, in order to provide phase diagrams as a function of chain-substrate interaction and misfit. Analytic derivations of transition lines are also provided within the continuum approximation. Their predictions are shown to quantitatively account for the numerical results, thus showing the validity of the continuum approximation in the misfit range under consideration. The present study thus extends our knowledge of the FK model by specifically focusing on diatomic chains and brings new information on a potentially interesting system which experimentalists just start being able to synthesize--oxide chains on metal substrates.

  3. Modeling of single char combustion, including CO oxidation in its boundary layer

    Energy Technology Data Exchange (ETDEWEB)

    Lee, C.H.; Longwell, J.P.; Sarofim, A.F.

    1994-10-25

    The combustion of a char particle can be divided into a transient phase where its temperature increases as it is heated by oxidation, and heat transfer from the surrounding gas to an approximately constant temperature stage where gas phase reaction is important and which consumes most of the carbon and an extinction stage caused by carbon burnout. In this work, separate models were developed for the transient heating where gas phase reactions were unimportant and for the steady temperature stage where gas phase reactions were treated in detail. The transient char combustion model incorporates intrinsic char surface production of CO and CO{sub 2}, internal pore diffusion and external mass and heat transfer. The model provides useful information for particle ignition, burning temperature profile, combustion time, and carbon consumption rate. A gas phase reaction model incorporating the full set of 28 elementary C/H/O reactions was developed. This model calculated the gas phase CO oxidation reaction in the boundary layer at particle temperatures of 1250 K and 2500 K by using the carbon consumption rate and the burning temperature at the pseudo-steady state calculated from the temperature profile model but the transient heating was not included. This gas phase model can predict the gas species, and the temperature distributions in the boundary layer, the CO{sub 2}/CO ratio, and the location of CO oxidation. A mechanistic heat and mass transfer model was added to the temperature profile model to predict combustion behavior in a fluidized bed. These models were applied to data from the fluidized combustion of Newlands coal char particles. 52 refs., 60 figs.

  4. 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.

  5. Determination of oxidative stress and effect of erdosteine on rhinitis medicamentosa in a rat model.

    Science.gov (United States)

    Dokuyucu, Recep; Cevik, Cengiz; Ozler, Gul Soylu; Ozgur, Tumay; Arli, Cengiz; Sefil, Fatih; Yonden, Zafer

    2014-11-05

    We aimed to determine the presence of oxidative stress in rhinitis medicamentosa (RM) and to evaluate the effect of erdosteine (ED) on mucosal changes in a rat model. Twenty-four male rats were used in this experimental study. Three groups were created. Group 1 (n=8) was the control group. Two puffs of 0.05% oxymetazolin were sprayed into the nasal cavities of the remaining rats (n=16) three times daily for eight weeks. One of these 16 rats was scarified at the end of the eight weeks and examined to confirm the presence of RM. Seven of the remaining 16 rats were killed, and venous blood samples were taken (Group 2). Group 3 (n=8) received 10mg/kg of an ED suspension orally for seven days. All rats were put on formalin for light microscopy. The total antioxidant status (TAS) was similar in all groups (p=0.073). The total oxidative status (TOS) of the RM group was significantly higher than that of the control group and RM+ED group (Group 3) (p=0.003 and p=0.011, respectively). The pathological recovery of the nasal mucosa of the rats was similar in the RM+ED and control groups. The TOS was high in this RM rat model, and oxidative stress was associated with RM. ED significantly ameliorated nasal mucosal changes induced by RM, suggesting that oxidative stress may play an important role in the pathophysiology of this condition.

  6. A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

    Science.gov (United States)

    Hossaini, Ryan; Chipperfield, Martyn P.; Saiz-Lopez, Alfonso; Fernandez, Rafael; Monks, Sarah; Feng, Wuhu; Brauer, Peter; Glasow, Roland

    2016-12-01

    Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by 2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea-salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub-ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1-5 × 104 atoms cm-3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to 4320 Gg Cl/yr, sustaining a background surface [Cl] of methane sink of 12-13 Tg CH4/yr due the CH4 + Cl reaction ( 2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for 10 to >20% of total boundary layer CH4 oxidation in some locations.

  7. 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

  8. Soot formation and oxidation during bio-oil gasification:experiments and modeling

    Institute of Scientific and Technical Information of China (English)

    Younes; Chhiti; Marine; Peyrot; Sylvain; Salvador

    2013-01-01

    A model is proposed to describe soot formation and oxidation during bio-oil gasification.It is based on the description of bio-oil heating,devolatilization,reforming of gases and conversion of both char and soot solids.Detailed chemistry (159 species and 773 reactions) is used in the gas phase.Soot production is described by a single reaction based on C2H2species concentration and three heterogeneous soot oxidation reactions.To support the validation of the model,three sets of experiments were carried out in a lab-scale Entrained Flow Reactor (EFR) equipped with soot quantification device.The temperature was varied from 1000 to 1400 C and three gaseous atmospheres were considered:default of steam,large excess of steam(H2O/C=8),and the presence of oxygen in the O/C range of 0.075–0.5.The model is shown to accurately describe the evolution of the concentration of the main gas species and to satisfactorily describe the soot concentration under the three atmospheres using a single set of identified kinetic parameters.Thanks to this model the contribution of different mechanisms involved in soot formation and oxidation in various situations can be assessed.

  9. Oxidation of Carbon Fibers in a Cracked Ceramic Matrix Composite Modeled as a Function of Temperature

    Science.gov (United States)

    Halbig, Michael C.; Cawley, James D.; Eckel, Andrew J.

    2003-01-01

    The oxidation model simulates the oxidation of the reinforcing carbon fibers within a ceramic matrix composite material containing as-fabricated microcracks. The physics-based oxidation model uses theoretically and experimentally determined variables as input for the model. The model simulates the ingress of oxygen through microcracks into a two-dimensional plane within the composite material. Model input includes temperature, oxygen concentration, the reaction rate constant, the diffusion coefficient, and the crack opening width as a function of the mechanical and thermal loads. The model is run in an iterative process for a two-dimensional grid system in which oxygen diffuses through the porous and cracked regions of the material and reacts with carbon in short time steps. The model allows the local oxygen concentrations and carbon volumes from the edge to the interior of the composite to be determined over time. Oxidation damage predicted by the model was compared with that observed from microstructural analysis of experimentally tested composite material to validate the model for two temperatures of interest. When the model is run for low-temperature conditions, the kinetics are reaction controlled. Carbon and oxygen reactions occur relatively slowly. Therefore, oxygen can bypass the carbon near the outer edge and diffuse into the interior so that it saturates the entire composite at relatively high concentrations. The kinetics are limited by the reaction rate between carbon and oxygen. This results in an interior that has high local concentrations of oxygen and a similar amount of consumed carbon throughout the cross section. When the model is run for high-temperature conditions, the kinetics are diffusion controlled. Carbon and oxygen reactions occur very quickly. The carbon consumes oxygen as soon as it is supplied. The kinetics are limited by the relatively slow rate at which oxygen is supplied in comparison to the relatively fast rate at which carbon and

  10. Oxidative stress is increased in C. elegans models of Huntington's disease but does not contribute to polyglutamine toxicity phenotypes.

    Science.gov (United States)

    Machiela, Emily; Dues, Dylan J; Senchuk, Megan M; Van Raamsdonk, Jeremy M

    2016-12-01

    Huntington's disease (HD) is an adult onset neurodegenerative disorder for which there is currently no cure. While HD patients and animal models of the disease exhibit increased oxidative damage, it is currently uncertain to what extent oxidative stress contributes to disease pathogenesis. In this work, we use a genetic approach to define the role of oxidative stress in HD. We find that a C. elegans model of HD expressing a disease-length polyglutamine tract in the body wall muscle is hypersensitive to oxidative stress and shows an upregulation of antioxidant defense genes, indicating that the HD worm model has increased levels of oxidative stress. To determine whether this increase in oxidative stress contributes to the development of polyglutamine-toxicity phenotypes in this HD model, we examined the effect of deleting individual superoxide dismutase (sod) genes in the HD worm model. As predicted, we found that deletion of sod genes in the HD worm model resulted in a clear increase in sensitivity to oxidative stress. However, we found that increasing oxidative stress in the HD worm model did not exacerbate deficits caused by polyglutamine toxicity. We confirmed these observations in two worm models expressing disease-length polyglutamine tracts in neurons. Furthermore, we found that treatment with antioxidants failed to rescue movement deficits or decrease aggregation in HD worm models. Combined, this suggests that the increase in oxidative stress in worm models of HD does not contribute to the phenotypic deficits observed in these worms, and provides a possible explanation for the failure of antioxidants in HD clinical trials.

  11. Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

    Science.gov (United States)

    Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

    2013-02-21

    A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

  12. Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2017-01-01

    Hydrogen isocyanide (HNC) has been proposed as an important intermediate in oxidation of hydrogen cyanide (HCN) in combustion, but details of its chemistry are still in discussion. At higher temperatures, HCN and HNC equilibrate rapidly, and being more reactive than HCN, HNC offers a fast...... alternative route of oxidation for cyanides. However, in previous modeling, it has been required to omit the HNC subset partly or fully in the reaction mechanisms to obtain satisfactory predictions. In the present work, we re-examine the chemistry of HNC and its role in combustion nitrogen chemistry. The HNC...... + O2 reaction is studied by ab initio methods and is shown to have a high barrier. Consequently, the omission of this reaction in recent modeling studies is justified. With the present knowledge of the HNC chemistry, including an accurate value of the heat of formation for HNC and improved rate...

  13. A comprehensive model for the supported vanadium oxide catalyst: The umbrella model

    NARCIS (Netherlands)

    Lingen, J.N.J. van

    2006-01-01

    Supported vanadium oxide catalysts are widely used in industry. However, the molecular structure of the active species, responsible for the actual catalysis, is for a large part still unknown. This thesis describes four years study on the elucidation of this molecular structure. It mainly focuses on

  14. 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 ...

  15. A Two-Dimensional, Finite-Difference Model of the Oxidation of a Uranium Carbide Fuel Pellet

    OpenAIRE

    Shepherd, J; Fairweather, M; Hanson, BC; Heggs, PJ

    2015-01-01

    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...

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

    Directory of Open Access Journals (Sweden)

    M. Lazaridis

    2005-01-01

    Full Text Available 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.

  17. Metallothionein-1 and nitric oxide expression are inversely correlated in a murine model of Chagas disease

    OpenAIRE

    2014-01-01

    Chagas disease, caused by Trypanosoma cruzi, represents an endemic among Latin America countries. The participation of free radicals, especially nitric oxide (NO), has been demonstrated in the pathophysiology of seropositive individuals with T. cruzi. In Chagas disease, increased NO contributes to the development of cardiomyopathy and megacolon. Metallothioneins (MTs) are efficient free radicals scavengers of NO in vitro and in vivo. Here, we developed a murine model of the chronic phase of C...

  18. 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 stor...... model for a commercially available 13Ah high-power lithium titanate oxide battery cell based on laboratory-performed extended characterization tests....

  19. Simulation of polyethylene oxide : improved structure using better models for hydrogen and flexible walls.

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J. W.; Duan, Y.; Nielsen, B.; Redfern, P. C.; Curtiss, L. A.; Univ. of Minnesota

    2001-08-22

    We describe calculations of the structure of amorphous polyethylene oxide using a previously reported model, but with better treatment of hydrogen positions and in a code which allows relaxation of stresses in the polymerized sample by Rahman-Parrinello techniques. We also report the effects of two different intermolecular force field potentials and find that our earlier, empirical force field produces better agreement with experimental neutron scattering results than a force field derived from ab initio electronic structure calculations.

  20. 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,...... 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....

  1. Dielectric Relaxation of Lanthanide-Based Ternary Oxides: Physical and Mathematical Models

    Directory of Open Access Journals (Sweden)

    Chun Zhao

    2012-01-01

    Full Text Available Cerium-doped hafnium oxides (CexHf1−xO2 and lanthanum-doped zirconium oxides (LaxZr1−xO2 were investigated. The highest dielectric constants, k, were obtained from lightly doped oxides with an La content of x=0.09 and a Ce content of x=0.1, for which k-values of 33~40 were obtained. The dielectric relaxation appears to be related to the size of crystal grains formed during annealing, which was dependent on the doping level. The physical and mathematical models were used to analyze the relationship between k-values and frequencies. The variations in the k-values up to megahertz frequencies for both CexHf1−xO2 and LaxZr1−xO2 are simulated based on the Curie-von Schweidler (CS or Havriliak-Negami (HN relationships. Concerning the lightly doped CexHf1−xO2 and LaxZr1−xO2, the data extracted are best modeled by the HN law, while LaxZr1−xO2 with doping level from x=0.22 to 0.63 are best modelled based on the CS law.

  2. Pyrite oxidation in saturated and Unsaturated Porous Media Flow: AComparison of alternative mathematical modeling approaches

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; White, Stephen P.; Pruess, Karsten

    1998-02-15

    Pyrite (FeS{sub 2}) is one of the most common naturally occurring minerals that is present in many subsurface environments. It plays an important role in the genesis of enriched ore deposits through weathering reactions, is the most abundant sulfide mineral in many mine tailings, and is the primary source of acid drainage from mines and waste rock piles. The pyrite oxidation reaction serves as a prototype for oxidative weathering processes with broad significance for geoscientific, engineering, and environmental applications. Mathematical modeling of these processes is extremely challenging because aqueous concentrations of key species vary over an enormous range, oxygen inventory and supply are typically small in comparison to pyrite inventory, and chemical reactions are complex, involving kinetic control and microbial catalysis. We present the mathematical formulation of a general multi-phase advective-diffusive reactive transport model for redox processes. Two alternative implementations were made in the TOUGHREACT and TOUGH2-CHEM simulation codes which use sequential iteration and simultaneous solution, respectively. The simulators are applied to reactive consumption of pyrite in (1) saturated flow of oxidizing water, and (2) saturated-unsaturated flow in which oxygen transport occurs in both aqueous and gas phases. Geochemical evolutions predicted from different process models are compared, and issues of numerical accuracy and efficiency are discussed.

  3. Evaluation of Toxicity Ranking for Metal Oxide Nanoparticles via an in Vitro Dosimetry Model.

    Science.gov (United States)

    Liu, Rong; Liu, Haoyang Haven; Ji, Zhaoxia; Chang, Chong Hyun; Xia, Tian; Nel, Andre E; Cohen, Yoram

    2015-09-22

    It has been argued that in vitro toxicity testing of engineered nanoparticles (NPs) should consider delivered dose (i.e., NP mass settled per suspension volume) rather than relying exclusively on administered dose (initial NP mass concentration). Delivered dose calculations require quantification of NP sedimentation in tissue cell culture media, taking into consideration fundamental suspension properties. In this article, we calculate delivered dose using a first-principles "particles in a box" sedimentation model, which accounts for the particle size distribution, fractal dimension, and permeability of agglomerated NPs. The sedimentation model was evaluated against external and our own experimental sedimentation data for metal oxide NPs. We then utilized the model to construct delivered dose-response analysis for a library of metal oxide NPs (previously used for hazard ranking and prediction making) in different cell culture media. Hierarchical hazard ranking of the seven (out of 24) toxic metal oxide NPs in our library, using EC50 calculated on the basis of delivered dose, did not measurably differ from our ranking based on administered dose. In contrast, simplified sedimentation calculations based on the assumption of impermeable NP agglomerates of a single average size significantly underestimated the settled NPs' mass, resulting in misinterpretation of toxicity ranking. It is acknowledged that in vitro dose-response outcomes are likely to be shaped by complex toxicodynamics, which include NP/cellular association, triggering of dynamic cell response pathways involved in NP uptake, and multiple physicochemical parameters that influence NP sedimentation and internalization.

  4. 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.

  5. Fuzzy Neural Network Model of 4-CBA Concentration for Industrial Purified Terephthalic Acid Oxidation Process

    Institute of Scientific and Technical Information of China (English)

    刘瑞兰; 苏宏业; 牟盛静; 贾涛; 陈渭泉; 褚健

    2004-01-01

    A fuzzy neural network (FNN) model is developed to predict the 4-CBA concentration of the oxidation unit in purified terephthalic acid process. Several technologies are used to deal with the process data before modeling.First,a set of preliminary input variables is selected according to prior knowledge and experience. Secondly,a method based on the maximum correlation coefficient is proposed to detect the dead time between the process variables and response variables. Finally, the fuzzy curve method is used to reduce the unimportant input variables.The simulation results based on industrial data show that the relative error range of the FNN model is narrower than that of the American Oil Company (AMOCO) model. Furthermore, the FNN model can predict the trend of the 4-CBA concentration more accurately.

  6. 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.

  7. 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.

  8. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Haouech, L.; Sperandio, M.; Cock, A.; Shayeb, H.

    2009-07-01

    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.

  10. 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.

  11. 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.

  12. Shock-tube and modeling study of ethane pyrolysis and oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Hidaka, Yoshiaki; Sato, Kazutaka; Hoshikawa, Hiroki; Nishimori, Toshihide; Takahashi, Rie; Tanaka, Hiroya; Inami, Koji; Ito, Nobuhiro

    2000-02-01

    Pyrolysis and oxidation of ethane were studied behind reflected shock waves in the temperature range 950--1,900 K at pressures of 1.2--4.0 atm. Ethane decay rates in both pyrolysis and oxidation were measured using time-resolved infrared (IR) laser absorption at 3.39 {micro}m, and CO{sub 2} production rates in oxidation were measured by time-resolved thermal IR emission at 4.24 {micro}m. The product yields were also determined using a single-pulse method. The pyrolysis and oxidation of ethane were modeled using a reaction mechanism with 157 reaction steps and 48 species including the most recent submechanisms for formaldehyde, ketene, methane, acetylene, and ethylene oxidation. The present and previously reported shock tube data were reproduced using this mechanism. The rate constants of the reactions C{sub 2}H{sub 6} {yields} CH{sub 3} + CH{sub 3}, C{sub 2}H{sub 5} + H {yields} H{sub 2} and C{sub 2}H{sub 5} + O{sub 2} {yields} C{sub 2}H{sub 4} + HO{sub 2} were evaluated. These reactions were important in predicting the previously reported and the present data, which were for mixture compositions ranging from ethane-rich (including ethane pyrolysis) to ethane-lean. The evaluated rate constants of the reactions C{sub 2}H{sub 5} + H {yields} C{sub 2}H{sub 4} + H{sub 2} and C{sub 2}H{sub 5} + O{sub 2} {yields} C{sub 2}H{sub 4} + HO{sub 2} were found to be significantly different from currently accepted values.

  13. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  14. 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

    2015-03-01

    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.

  15. Kinetic model of the inhibition of respiration by endogenous nitric oxide in intact cells.

    Science.gov (United States)

    Aguirre, Enara; Rodríguez-Juárez, Félix; Bellelli, Andrea; Gnaiger, Erich; Cadenas, Susana

    2010-05-01

    Nitric oxide (NO) inhibits mitochondrial respiration by decreasing the apparent affinity of cytochrome c oxidase (CcO) for oxygen. Using iNOS-transfected HEK 293 cells to achieve regulated intracellular NO production, we determined NO and O(2) concentrations and mitochondrial O(2) consumption by high-resolution respirometry over a range of O(2) concentrations down to nanomolar. Inhibition of respiration by NO was reversible, and complete NO removal recovered cell respiration above its routine reference values. Respiration was observed even at high NO concentrations, and the dependence of IC(50) on [O(2)] exhibits a characteristic but puzzling parabolic shape; both these features imply that CcO is protected from complete inactivation by NO and are likely to be physiologically relevant. We present a kinetic model of CcO inhibition by NO that efficiently predicts experimentally determined respiration at physiological O(2) and NO concentrations and under hypoxia, and accurately predicts the respiratory responses under hyperoxia. The model invokes competitive and uncompetitive inhibition by binding of NO to the reduced and oxidized forms of CcO, respectively, and suggests that dissociation of NO from reduced CcO may involve its O(2)-dependent oxidation. It also explains the non-linear dependence of IC(50) on O(2) concentration, and the hyperbolic increase of c(50) as a function of NO concentration.

  16. 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

  17. Mathematical model of a plate fin heat exchanger operating under solid oxide fuel cell working conditions

    Science.gov (United States)

    Kaniowski, Robert; Poniewski, Mieczysław

    2013-12-01

    Heat exchangers of different types find application in power systems based on solid oxide fuel cells (SOFC). Compact plate fin heat exchangers are typically found to perfectly fit systems with power output under 5 kWel. Micro-combined heat and power (micro-CHP) units with solid oxide fuel cells can exhibit high electrical and overall efficiencies, exceeding 85%, respectively. These values can be achieved only when high thermal integration of a system is assured. Selection and sizing of heat exchangers play a crucial role and should be done with caution. Moreover, performance of heat exchangers under variable operating conditions can strongly influence efficiency of the complete system. For that reason, it becomes important to develop high fidelity mathematical models allowing evaluation of heat exchangers under modified operating conditions, in high temperature regimes. Prediction of pressure and temperatures drops at the exit of cold and hot sides are important for system-level studies. Paper presents dedicated mathematical model used for evaluation of a plate fin heat exchanger, operating as a part of micro-CHP unit with solid oxide fuel cells.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. Paeoniflorin Attenuated Oxidative Stress in Rat COPD Model Induced by Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Jinpei Lin

    2016-01-01

    Full Text Available Paeoniflorin (PF, a monoterpene glucoside, might have an effect on the oxidative stress. However, the mechanism is still unknown. In this study, we made the COPD model in Sprague-Dawley (SD rats by exposing them to the smoke of 20 cigarettes for 1 hour/day and 6 days/week, for 12 weeks, 24 weeks, or 36 weeks. Our findings suggested that smoke inhalation can trigger the oxidative stress from the very beginning. A 24-week treatment of PF especially in the dosage of 40 mg/kg·d can attenuate oxygen stress by partially quenching reactive oxygen species (ROS and upregulating antioxidant enzymes via an Nrf2-dependent mechanism.

  3. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues-Model Compounds Targeting Oxidative Stress.

    Science.gov (United States)

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry.

  4. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Astrida Velena

    2016-01-01

    Full Text Available Many 1,4-dihydropyridines (DHPs possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA. Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL, mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry.

  5. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

    Science.gov (United States)

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry. PMID:26881016

  6. Hydroxycitric acid ameliorates inlfammation and oxidative stress in mouse models of multiple sclerosis

    Institute of Scientific and Technical Information of China (English)

    Mahdi Goudarzvand; Shahin Khadem Azarian; Abbas Mirshaifey; Gholamreza Azizi; Sanaz Afraei; Somaye Yaslianifard; Saleh Ghiasy; Ghazal Sadri; Mustafa Kalvandi; Tina Alinia; Ali Mohebbi; Reza Yazdani

    2016-01-01

    Hydroxycitric acid (HCA) is derived primarily from the Garcinia plant and is widely used for its anti-in-lfammatory effects. Multiple sclerosis can cause an inlfammatory demyelination and axonal damage. In this study, to validate the hypothesis that HCA exhibits therapeutic effects on multiple sclerosis, we established female C57BL/6 mouse models of multiple sclerosis,i.e., experimental autoimmune encephalomyelitis, using Complete Freund’s Adjuvant (CFA) emulsion containing myelin oligodendrocyte glycoprotein (35–55). Treatment with HCA at 2 g/kg/d for 3 weeks obviously improved the symptoms of nerve injury of experimental autoimmune encephalomyelitis mice, decreased serum interleulin-6, tumor necrosis factor alpha, nitric oxide, and malondialdehyde levels, and increased superoxide dismutase and glutathione reduc-tase activities. hTese ifndings suggest that HCA exhibits neuroprotective effects on multiple sclerosis-caused nerve injury through ameliorating inlfammation and oxidative stress.

  7. 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

    2006-03-05

    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.

  8. 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

  9. Sensitivity analysis in oxidation ditch modelling: the effect of variations in stoichiometric, kinetic and operating parameters on the performance indices

    NARCIS (Netherlands)

    Abusam, A.A.A.; Keesman, K.J.; Straten, van G.; Spanjers, H.; Meinema, K.

    2001-01-01

    This paper demonstrates the application of the factorial sensitivity analysis methodology in studying the influence of variations in stoichiometric, kinetic and operating parameters on the performance indices of an oxidation ditch simulation model (benchmark). Factorial sensitivity analysis investig

  10. 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...

  11. The Interaction Between Lipoxygenase-Catalyzed Oxidation and Autoxidation in Dry-Cured Bacon and a Model System.

    Science.gov (United States)

    Zhang, Yingyang; Tang, Jing; Zhao, Jianying; Wu, Haizhou; Ditta, Yasir Allah; Zhang, Jianhao

    2015-12-01

    A model system was conducted to characterize the interaction between lipid autoxidation and enzyme-catalyzed oxidation in dry-cured bacon. This involved the use of a hydroxyl radical (HO•) generating system and the extraction and purification of lipoxygenases (LOX) from pork belly. The results showed that LOX activity rapidly (P bacon. This may be because of the hydroxyl-radical-mediated oxidation from LOX-Fe(2+) to LOX-Fe(3+), which activates LOX. In addition, experiments of the model system also showed that LOX activity could be inhibited by increasing the substrate concentration, although substrate type and concentration had no effect on autoxidation. Moreover, LOX enzyme-catalyzed oxidation and autoxidation could act synergistically to promote lipid oxidation irrespective of the substrate (linoleic or arachidonic acid). These results provide useful information for regulating lipid oxidation during the production of dry-cured pork products.

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

    Science.gov (United States)

    Sokhansanj, Bahrad A; Wilson, David M

    2004-08-01

    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 that vary over three to four 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 findings 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.

  13. The need for nano-scale modeling in solid oxide fuel cells.

    Science.gov (United States)

    Ryan, E M; Recknagle, K P; Liu, W; Khaleel, M A

    2012-08-01

    Solid oxide fuel cells (SOFCs) are high temperature fuel cells, which are being developed for large scale and distributed power systems. SOFCs promise to provide cleaner, more efficient electricity than traditional fossil fuel burning power plants. Research over the last decade has improved the design and materials used in SOFCs to increase their performance and stability for long-term operation; however, there are still challenges for SOFC researchers to overcome before SOFCs can be considered competitive with traditional fossil fuel burning and renewable power systems. In particular degradation due to contaminants in the fuel and oxidant stream is a major challenge facing SOFCs. In this paper we discuss ongoing computational and experimental research into different degradation and design issues in SOFC electrodes. We focus on contaminants in gasified coal which cause electrochemical and structural degradation in the anode, and chromium poisoning which affects the electrochemistry of the cathode. Due to the complex microstructures and multi-physics of SOFCs, multi-scale computational modeling and experimental research is needed to understand the detailed physics behind different degradation mechanisms, the local conditions within the cell which facilitate degradation, and its effects on the overall SOFC performance. We will discuss computational modeling research of SOFCs at the macro-, meso- and nano-scales which is being used to investigate the performance and degradation of SOFCs. We will also discuss the need for a multi-scale modeling framework of SOFCs, and the application of computational and multi-scale modeling to several degradation issues in SOFCs.

  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. 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.

  16. Metal oxide-graphene field-effect transistor: interface trap density extraction model

    Directory of Open Access Journals (Sweden)

    Faraz Najam

    2016-09-01

    Full Text Available A simple to implement model is presented to extract interface trap density of graphene field effect transistors. The presence of interface trap states detrimentally affects the device drain current–gate voltage relationship Ids–Vgs. At the moment, there is no analytical method available to extract the interface trap distribution of metal-oxide-graphene field effect transistor (MOGFET devices. The model presented here extracts the interface trap distribution of MOGFET devices making use of available experimental capacitance–gate voltage Ctot–Vgs data and a basic set of equations used to define the device physics of MOGFET devices. The model was used to extract the interface trap distribution of 2 experimental devices. Device parameters calculated using the extracted interface trap distribution from the model, including surface potential, interface trap charge and interface trap capacitance compared very well with their respective experimental counterparts. The model enables accurate calculation of the surface potential affected by trap charge. Other models ignore the effect of trap charge and only calculate the ideal surface potential. Such ideal surface potential when used in a surface potential based drain current model will result in an inaccurate prediction of the drain current. Accurate calculation of surface potential that can later be used in drain current model is highlighted as a major advantage of the model.

  17. Time-Dependent and Light-Induced Fading in Victoreen Model 2600-80 Aluminum Oxide Thermoluminescence Dosemeters

    Science.gov (United States)

    1993-01-01

    2600-80 Aluminium Oxide Thermoluminescence Dosemeters ":"TIC,7 • :+ " 7-t-•CTE S , E 1P 1993 F’ t LEA l E J. H. Musk AFRRI TR93-6 Cleared for Public...SUBTITLE 5. FUNDING NUMBERS Time-Dependent and Light-Induced Fading in Victoreen0 Model 2600-80 Aluminium Oxide Thermoluminescence PE: QAXM...MODEL 2600-80 ALUMINIUM OXIDE THERMOLUMINESCENCE DOSEMETERS J. H. Musk Accesion For NTIS CRA&I DTIC TAB U.,announced D Justification ........ -.. By

  18. 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.

  19. 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

  20. Mesoscale modeling of combined aerosol and photo-oxidant processes in the eastern Mediterranean

    Directory of Open Access Journals (Sweden)

    M. Lazaridis

    2004-09-01

    Full Text Available 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. 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 but better comparison has been obtained for the winter data.

  1. Estimating reaction constants by ab initio molecular modeling: a study on the oxidation of phenol to catechol and hydroquinone in advanced oxidation processes

    Directory of Open Access Journals (Sweden)

    B. Ramos

    2012-03-01

    Full Text Available Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

  2. 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.

  3. Paraoxonase and Arylesterase Activities, Lipid Profile, and Oxidative Damage in Experimental Ischemic Colitis Model

    Directory of Open Access Journals (Sweden)

    Ethem Unal

    2012-01-01

    Full Text Available Objective. In the present study, since PON1 is known as an HDL-associated antioxidant enzyme that inhibits the oxidative modification of LDL and oxidative stress plays a role in the pathogenesis of mesenteric ischemia, we investigated the changes in PON1 activity and lipid profile in an experimental ischemic colitis model. Methods. Forty male Wistar albino rats were divided into two groups: the control group (N=15 and the experimental group (N=25. All animals were anesthetized with ether and ketamine anesthesia to undergo a midline laparotomy. Ischemic colitis was induced by marginal vessel ligation in the splenic flexura (devascularization process. A sham laparotomy was performed in the control group. All animals were sacrificed on the seventh postoperative day. Oxidative stress marker (malonyldialdehyde, MDA, lipid profile, and paraoxonase (PON-1 and arylesterase activities were determined. Histopathological evaluation was done under light microscopy, after sectioning and staining with hematoxyline and eosin. Statistical analysis was conducted using Student’s t-test and Mann-Whitney U test, and P0.05. Conclusions. PON1 and arylesterase play an important role in the pathophysiology of ischemic colitis.

  4. 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.

  5. 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...... fraction. The inactive biomass fraction consists of exocellular polymers and biodegradable and inert particulate biomass. The model describes the oxygen respiration in detail. Yield coefficients, decay constants and hydrolysis constants are estimated based on the oxygen respiration. An analysis...... of the observability of the system reveals that several of the coefficients cannot be determined explicitly due to the complexity of the model and the limited amount of variables measured. Estimation procedures based on least squares methods are employed and parameter estimates and confidence intervals are computed...

  6. Ionic Model of Some Aspects of Cu NQR Spectra in Superconducting Oxides

    Science.gov (United States)

    Shimizu, Tadashi

    1993-02-01

    We apply an ionic model to explain the pressure and the temperature dependences of copper nuclear quadrupole frequency νQ in superconducting oxides. The pressure and the temperature dependences of νQ can, for the most part, be explained only by the change in the lattice spacing. It has also been shown that the origin of large difference in the 63Cu NQR line width between crystallographically different copper sites in YBa2Cu3O6.5 can be explained in the same model. The result of the present study suggests that the Sternheimer antishielding factor γ∞ is certainly effective in the case of ionic model, although a negligibly small value has been argued from viewpoint of the band calculation.

  7. 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.

  8. Early life and oxidative stress in psychiatric disorders: what can we learn from animal models?

    Science.gov (United States)

    Mhillaj, Emanuela; Morgese, Maria Grazia; Trabace, Luigia

    2015-01-01

    Schizophrenia is a complex pathology characterized by the occurrence of a variety of symptoms classified as positive, negative and cognitive. Although the exact etiopathogenesis of this disorder has not been unraveled yet, many theories have been endorsed during the last years. Among these, the neurochemical theories have been the most suited, considering the dopaminergic and glutamatergic dysfunctions to be mainly responsible for psychotic symptoms. However, the lack of efficacy of the available drugs, namely antipsychotics, toward negative and cognitive symptoms led to hypothesize alternative approaches. In this regard, the neurodevelopmental theory of schizophrenia has emerged, proposing the association between the occurrence of environmental risk factors in early-life and the development of psychosis in late-life. In particular, exposure to early life stressing situations, such as pre- and peri-natal stress, has been suggested as a risk factor to d evelop psychopathologies in adulthood in people genetically predisposed. A crucial support in favor of this hypothesis came from neurodevelopmental animal models of schizophrenia, such as maternal malnutrition, maternal deprivation, maternal infections as well as post-weaning social isolation rearing. Moreover, data from these models, corroborated by clinical findings, indicate that oxidative and nitrosative stress play a crucial role in the etiopathogenesis of psychiatric disorders. In the present work, we reviewed the recent progress in literature regarding data available from animal models linking oxidative and nitrosative stress to psychiatric disorders in order to evaluate novel biomarkers of pathology as well as novel therapeutical targets.

  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. 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.

  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. Modeling, control and integration of a portable solid oxide fuel cell system

    Science.gov (United States)

    Adhikari, Puran

    This thesis presents an innovative method for the modeling, control and integration of a portable hybrid solid oxide fuel cell system. The control and integration of the fuel cell system is important not only for its efficient operation, but also for issues related to safety and reliability. System modeling is needed in order to facilitate the controller design. Mathematical models of the various components of the system are built in the matlab/simulink environment. Dynamic modeling of the fuel cell stack, catalytic partial oxidation (CPOX) reformer, heat exchanger, tail gas combustor and tail gas splitter of the balance of plant system is performed first. Followed by, modeling of the three input DC/DC converter and energy storage devices (battery and supercapacitor). A two-level control approach, higher level and lower level, is adopted in this research. Each of the two major subsystems, balance of plant subsystem and power electronics subsystem, has its own local level controller (called lower level controller) that are designed such that they follow exactly the command reference from a higher level controller. The higher level controller is an intelligent controller that makes decisions about how the lower level or local controllers should perform based on the status of fuel cell, energy storage device and external load demand. Linear analysis has been done for the design and development of the local controllers as appropriate. For the higher level controller, a finite state machine model is developed and implemented using stateflow and fuzzy logic toolboxes of matlab. Simulations are carried out for the integrated system. The simulation results verify that the controllers are robust in performance during the transient condition when the energy storage devices supplement fuel cells. The temperature and flow rates of the fuel and air are controlled as desired. The output from the designed fuel cell system is a regulated DC voltage, which verifies the overall

  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. Measurement-based modelling of bromine-induced oxidation of mercury above the Dead Sea

    Science.gov (United States)

    Tas, E.; Obrist, D.; Peleg, M.; Matveev, V.; Faïn, X.; Asaf, D.; Luria, M.

    2012-03-01

    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 oxidation at the Dead Sea does not critically depend on Br and, therefore, is comparable to that in cold polar regions. In order to confirm the suggested kinetics, additional studies, particularly for temperature-dependence of rate constants, are required.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. Investigations on boron carbide oxidation for nuclear reactors safety-General modelling for ICARE/CATHARE code applications

    Energy Technology Data Exchange (ETDEWEB)

    Seiler, N. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Cadarache, BP 3, 13 115 Saint Paul lez Durance Cedex (France)], E-mail: nathalie.seiler@irsn.fr; Bertrand, F.; Marchand, O.; Repetto, G. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Cadarache, BP 3, 13 115 Saint Paul lez Durance Cedex (France); Ederli, S. [ENEA, Ente per le Nuove Tecnologie l' Energia et l' Ambiente (Italy)

    2008-04-15

    The present paper deals with the problem of boron carbide pellet oxidation which might occur during a severe accident. A basic correlation, involving global variables, has been developed for the simulation of boron carbide oxidation with the ICARE/CATHARE code. This modelling has been based on available experimental data, including the VERDI separate effects experiments performed by IRSN at low pressures and high temperatures. According to the agreement between the measured and the calculated bundle temperatures as well as hydrogen release and oxidized B{sub 4}C, the ICARE/CATHARE code simulates rather well QUENCH experiments involving B{sub 4}C control rod degradation, Zircaloy oxidation under starvation and cooling with steam. Based on simulations results, it has been noticed that the B{sub 4}C degradation has a slight direct effect on global bundle degradation but a non-negligible influence on Zircaloy oxidation through power release, material melting and flowing down.

  20. 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.

  1. Accurate geometry scalable complementary metal oxide semiconductor modelling of low-power 90 nm amplifier circuits

    Directory of Open Access Journals (Sweden)

    Apratim Roy

    2014-05-01

    Full Text Available This paper proposes a technique to accurately estimate radio frequency behaviour of low-power 90 nm amplifier circuits with geometry scalable discrete complementary metal oxide semiconductor (CMOS modelling. Rather than characterising individual elements, the scheme is able to predict gain, noise and reflection loss of low-noise amplifier (LNA architectures made with bias, active and passive components. It reduces number of model parameters by formulating dependent functions in symmetric distributed modelling and shows that simple fitting factors can account for extraneous (interconnect effects in LNA structure. Equivalent-circuit model equations based on physical structure and describing layout parasites are developed for major amplifier elements like metal–insulator–metal (MIM capacitor, spiral symmetric inductor, polysilicon (PS resistor and bulk RF transistor. The models are geometry scalable with respect to feature dimensions, i.e. MIM/PS width and length, outer-dimension/turns of planar inductor and channel-width/fingers of active device. Results obtained with the CMOS models are compared against measured literature data for two 1.2 V amplifier circuits where prediction accuracy for RF parameters (S(21, noise figure, S(11, S(22 lies within the range of 92–99%.

  2. 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.

  3. Modeling and optimization of the combined carbon dioxide reforming and partial oxidation of natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Larentis, A.L.; De Resende, N.S.; Salim, V.M.M.; Pinto, J.C. [Programa de Engenharia Quimica/COPPE/Universidade Federal do Rio de Janeiro, Cidade Universitaria, CP 68502, RJ, 21945-970 Rio de Janeiro (Brazil)

    2001-07-13

    The optimization of the combined carbon dioxide reforming and partial methane oxidation over a 1% Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied in order to produce synthesis gas with hydrogen/carbon monoxide ratio close to 1, for applications in metallurgical and polycarbonates processes and for production of oxygenated compounds and hydrocarbons. The study was performed with the help of experimental design and two mathematical modeling approaches: empirical and phenomenological. Empirical polynomial models were employed to analyze the effects of the process variables on the response factors and the final correlation coefficients obtained were above 95%. The phenomenological model was obtained from individual mass balances and the obtained correlation coefficients were above 95% for CH{sub 4} and N{sub 2}, 90% for CO{sub 2} and H{sub 2}O and near 70% for H{sub 2} and CO. The empirical modeling approach was found to be more efficient, simpler and led to better results than those obtained with the phenomenological model approach. Therefore, the empirical modeling was used for optimization of the process operation conditions. At an oxygen/methane ratio of 0.55gmol/gmol and temperature of 950C, optimized process conditions were obtained with complete methane conversion, maximum carbon monoxide selectivity of 43% and minimum hydrogen/carbon monoxide ratio of 1.3, in absence of water.

  4. A Microscale Modeling Tool for the Design and Optimization of Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Shixue Liu

    2009-06-01

    Full Text Available A two dimensional numerical model of a solid oxide fuel cell (SOFC with electrode functional layers is presented. The model incorporates the partial differential equations for mass transport, electric conduction and electrochemical reactions in the electrode functional layers, the anode support layer, the cathode current collection layer and at the electrode/electrolyte interfaces. A dusty gas model is used in modeling the gas transport in porous electrodes. The model is capable of providing results in good agreement with the experimental I-V relationship. Numerical examples are presented to illustrate the applications of this numerical model as a tool for the design and optimization of SOFCs. For a stack assembly of a pitch width of 2 mm and an interconnect-electrode contact resistance of 0.025 Ωcm2, a typical SOFC stack cell should consist of a rib width of 0.9 mm, a cathode current collection layer thickness of 200–300 μm, a cathode functional layer thickness of 20–40 μm, and an anode functional layer thickness of 10–20 μm in order to achieve optimal performance.

  5. 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.)

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Gelß, Patrick, E-mail: p.gelss@fu-berlin.de; Matera, Sebastian, E-mail: matera@math.fu-berlin.de; Schütte, Christof, E-mail: schuette@mi.fu-berlin.de

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO{sub 2}(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  11. Model of porous aluminium oxide growth during initial stage of anodization

    Science.gov (United States)

    Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

    2014-10-01

    Currently, the development of nanotechnology and metamaterials requires the ability to obtain regular self-assembled structures with different parameters. One such structure is porous alumina in which the pores grow perpendicular to the substrate and are hexagonally packed. Pore size and the distance between them can be varied depending on the anodization voltage, the electrolyte and the anodization time (pore diameter - from 2 to 350 nm, the distance between the pores - from 5 to 50 nm). At the moment, there are different models describing the process of anodizing aluminum, in this paper we propose a model that takes into account the effect of layers of aluminum, aluminum oxide, and the electrolyte, as well as the influence of the effect of surface diffusion.

  12. Estimation of component activities in some oxide solid solutions by the molecular interaction vacancy model

    Institute of Scientific and Technical Information of China (English)

    Dongping TAO

    2011-01-01

    The molecular interaction vacancy model (MIVM) is used to estimate simultaneously activities of all components in a range of entire composition of six binary oxide solid solutions and the MnO-FeO-CaO ternary solid solution by their binary infinite dilute activity coefficients.The average errors are the 0.03%-5.0% for the binaries and the 4.11%-25.2% for the ternary which is less than that (4.84%-41.2%) of the sub-regular solution model (SRSM).This shows that MIVM is more effective and reliable than SRSM for the ternary and does not depend on a polynomial approximation with some ternary adjustable parameters.

  13. Development of a charge-transfer distribution model for stack simulation of solid oxide fuel cells

    Science.gov (United States)

    Onaka, H.; Iwai, H.; Kishimoto, M.; Saito, M.; Yoshida, H.; Brus, G.; Szmyd, J. S.

    2016-09-01

    An overpotential model for planar solid oxide fuel cells (SOFCs) is developed and applied to a stack numerical simulation. Charge-transfer distribution within the electrodes are approximated using an exponential function, based on which the Ohmic loss and activation overpotential are evaluated. The predicted current-voltage characteristics agree well with the experimental results, and also the overpotentials within the cell can reproduce the results obtained from a numerical analysis where the distribution of the charge-transfer current within the electrodes is fully solved. The proposed model is expected to be useful to maintain the accuracy of SOFC simulations when the cell components, consisting of anode, electrolyte and cathode, are simplified into one layer element.

  14. SOLID OXIDE FUEL CELL CATHODES: Polarization Mechanisms and Modeling of the Electrochemical Performance

    Science.gov (United States)

    Fleig, Jurgen

    2003-08-01

    Several recent experimental and numerical investigations have contributed to the improved understanding of the electrochemical mechanisms taking place at solid oxide fuel cell (SOFC) cathodes and yielded valuable information on the relationships between alterable parameters (geometry/material) and the cathodic polarization resistance. Efforts to reduce the polarization resistance in SOFCs can benefit from these results, and some important aspects of the corresponding studies are reviewed. Experimental results, particularly measurements using geometrically well-defined Sr-doped LaMnO3 (LSM) cathodes, are discussed. In regard to simulations, the different levels of sophistication used in SOFC electrode modeling studies are summarized and compared. Exemplary simulations of mixed conducting cathodes that show the capabilities and limits of different modeling levels are described.

  15. 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.

  16. 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....

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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)

  3. 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)

  4. Modelling the descent of nitric oxide during the elevated stratopause event of January 2013

    Science.gov (United States)

    Orsolini, Yvan J.; Limpasuvan, Varavut; Pérot, Kristell; Espy, Patrick; Hibbins, Robert; Lossow, Stefan; Raaholt Larsson, Katarina; Murtagh, Donal

    2017-03-01

    Using simulations with a whole-atmosphere chemistry-climate model nudged by meteorological analyses, global satellite observations of nitrogen oxide (NO) and water vapour by the Sub-Millimetre Radiometer instrument (SMR), of temperature by the Microwave Limb Sounder (MLS), as well as local radar observations, this study examines the recent major stratospheric sudden warming accompanied by an elevated stratopause event (ESE) that occurred in January 2013. We examine dynamical processes during the ESE, including the role of planetary wave, gravity wave and tidal forcing on the initiation of the descent in the mesosphere-lower thermosphere (MLT) and its continuation throughout the mesosphere and stratosphere, as well as the impact of model eddy diffusion. We analyse the transport of NO and find the model underestimates the large descent of NO compared to SMR observations. We demonstrate that the discrepancy arises abruptly in the MLT region at a time when the resolved wave forcing and the planetary wave activity increase, just before the elevated stratopause reforms. The discrepancy persists despite doubling the model eddy diffusion. While the simulations reproduce an enhancement of the semi-diurnal tide following the onset of the 2013 SSW, corroborating new meteor radar observations at high northern latitudes over Trondheim (63.4°N), the modelled tidal contribution to the forcing of the mean meridional circulation and to the descent is a small portion of the resolved wave forcing, and lags it by about ten days.

  5. 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.

  6. 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.

  7. 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.

  8. 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...

  9. 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...

  10. 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.

  11. 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.

  12. Quantitative analysis of anaerobic oxidation of methane (AOM) in marine sediments: A modeling perspective

    Science.gov (United States)

    Regnier, P.; Dale, A. W.; Arndt, S.; LaRowe, D. E.; Mogollón, J.; Van Cappellen, P.

    2011-05-01

    Recent developments in the quantitative modeling of methane dynamics and anaerobic oxidation of methane (AOM) in marine sediments are critically reviewed. The first part of the review begins with a comparison of alternative kinetic models for AOM. The roles of bioenergetic limitations, intermediate compounds and biomass growth are highlighted. Next, the key transport mechanisms in multi-phase sedimentary environments affecting AOM and methane fluxes are briefly treated, while attention is also given to additional controls on methane and sulfate turnover, including organic matter mineralization, sulfur cycling and methane phase transitions. In the second part of the review, the structure, forcing functions and parameterization of published models of AOM in sediments are analyzed. The six-orders-of-magnitude range in rate constants reported for the widely used bimolecular rate law for AOM emphasizes the limited transferability of this simple kinetic model and, hence, the need for more comprehensive descriptions of the AOM reaction system. The derivation and implementation of more complete reaction models, however, are limited by the availability of observational data. In this context, we attempt to rank the relative benefits of potential experimental measurements that should help to better constrain AOM models. The last part of the review presents a compilation of reported depth-integrated AOM rates (ΣAOM). These rates reveal the extreme variability of ΣAOM in marine sediments. The model results are further used to derive quantitative relationships between ΣAOM and the magnitude of externally impressed fluid flow, as well as between ΣAOM and the depth of the sulfate-methane transition zone (SMTZ). This review contributes to an improved understanding of the global significance of the AOM process, and helps identify outstanding questions and future directions in the modeling of methane cycling and AOM in marine sediments.

  13. Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model – Part 1: Assessing the influence of constrained multi-generational ageing

    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

  14. The antagonism of cholecystokinin octapeptide-8 to the peroxynitrite oxidation on a diabetic cataractal rat model

    Institute of Scientific and Technical Information of China (English)

    HAO Li-na; LING Yi-qun; MAO Qi-yan; LING Yi-ling; HE Shou-zhi

    2006-01-01

    Background Cataracts is considered be formed because of an abnormal glucose metabolic pathway or oxidative stress. We explored the damaging role of ONOO- and antagonism of cholecystokinin octapeptide-8(CCK-8) in diabetic cataractal rat lenses.Methods A diabetic cataractal animal model was established by peritoneal injection of streptozotocine (STZ).Thirty-six normal SD rats were taken as control group; seventy-two were given STZ (45 mg/kg) and then divided into STZ group and CCK-8 group (peritoneal injection CCK-8). STZ induced diabetic rats were treated with CCK-8 for 60 days. Lenses were examined with slit lamp at 20, 40 and 60 days. Immunofluorescent staining and Western blot analysis were used for determining nitrotyrosine (NT, a marker for ONOO-). RT-PCR and gene array analysis were used for determining the expression of inducible nitric oxide synthetase mRNA (iNOS mRNA) in lens epithelium (LEC).Results STZ group rats developed lens opacity by 20 days that reached a high level by 60 days after STZ injection. CCK-8 group rats delayed the cataract formation. There was no distinct expression of NT and iNOS mRNA in control group. In STZ group, there were distinct expression of NT and upregulation of iNOS mRNA;however, CCK-8 group showed weak expression of NT and downregulation of iNOS mRNA.Conclusions NT, which may be a new form of oxidative stress, was expressed in diabetic rat LEC although CCK-8 could reverse NT damage in LEC. The results suggested that CCK-8 might be a useful therapeutic agent against diabetic cataract. The antagonizing mechanism of CCK-8 may be related to direct antagonism of ONOO-as well as its inhibition of the expression of iNOS mRNA for production of NO and therefore decrease in the formation of ONOO-.

  15. 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.

  16. 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%.

  17. 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.

  18. 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)

  19. Direct Observation of Enhanced Nitric Oxide in a Murine Model of Diabetic Nephropathy

    Science.gov (United States)

    Boels, Margien G. S.; van Faassen, Ernst E. H.; Avramut, M. Cristina; van der Vlag, Johan; van den Berg, Bernard M.; Rabelink, Ton J.

    2017-01-01

    Uncoupling of nitric oxide synthase (NOS) secondary to redox signaling is a central mechanism in endothelial and macrophage activation. To date studies on the production of nitric oxide (NO) during the development of diabetic complications show paradoxical results. We previously showed that recoupling eNOS by increasing the eNOS cofactor tetrahydrobiopterin (BH4) could restore endothelial function and prevent kidney injury in experimental kidney transplantation. Here, we employed a diabetic mouse model to investigate the effects of diabetes on renal tissue NO bioavailability. For this, we used in vivo NO trapping, followed by electron paramagnetic resonance spectroscopy. In addition, we investigated whether coupling of NOS by supplying the cofactor BH4 could restore glomerular endothelial barrier function. Our data show that overall NO availability at the tissue level is not reduced sixteen weeks after the induction of diabetes in apoE knockout mice, despite the presence of factors that cause endothelial dysfunction, and the presence of the endogenous NOS inhibitor ADMA. Targeting uncoupled NOS with the BH4 precursor sepiapterin further increases NO availability, but did not modify renal glomerular injury. Notably, glomerular heparanase activity as a driver for loss of glomerular barrier function was not reduced, pointing towards NOS-independent mechanisms. This was confirmed by unaltered increased glomerular presence of cathepsin L, the protease that activates heparanase. PMID:28103268

  20. Infliximab improves endothelial dysfunction in a mouse model of antiphospholipid syndrome: Role of reduced oxidative stress.

    Science.gov (United States)

    Benhamou, Ygal; Miranda, Sébastien; Armengol, Guillaume; Harouki, Najah; Drouot, Laurent; Zahr, Noel; Thuillez, Christian; Boyer, Olivier; Levesque, Hervé; Joannides, Robinson; Richard, Vincent

    2015-08-01

    Antiphospholipid syndrome (APS), induces endothelial dysfunction, oxidative stress and systemic inflammation that may be mediated by TNFα. Thus, we investigated the possible protective effect of the anti-TNFα antibody infliximab (5μg/g) on endothelial function in a mouse APS model (induced by injection of purified human anti-β2GP1-IgG). Seven days after anti-β2GPI-IgG injection, we observed an increase in plasma sVCAM-1 and sE-selectin levels and in aortic mRNA expression of VCAM-1 and E-selectin. This was associated with a decreased endothelium-dependent relaxation of isolated mesenteric arteries to acetylcholine, together with decreased mesenteric eNOS mRNA expression and increased eNOS uncoupling, accompanied by increased iNOS and gp91phox mRNA and increased left ventricular GSH/GSSH ratio. Infliximab significantly improved the NO-mediated relaxing responses to acetylcholine, and induced a decrease in iNOS and gp91phox mRNA expression. The õpro-adhesive and pro-coagulant phenotypes induced by the anti-β2GP1-IgG were also reversed. This study provides the first evidence that TNFα antagonism improves endothelial dysfunction in APS and suggests that endothelial dysfunction is mediated by TNFα and oxidative stress. Therefore, infliximab may be of special relevance in clinical practice.

  1. NMR Metabolomics Show Evidence for Mitochondrial Oxidative Stress in a Mouse Model of Polycystic Ovary Syndrome.

    Science.gov (United States)

    Selen, Ebru Selin; Bolandnazar, Zeinab; Tonelli, Marco; Bütz, Daniel E; Haviland, Julia A; Porter, Warren P; Assadi-Porter, Fariba M

    2015-08-07

    Polycystic ovary syndrome (PCOS) is associated with metabolic and endocrine disorders in women of reproductive age. The etiology of PCOS is still unknown. Mice prenatally treated with glucocorticoids exhibit metabolic disturbances that are similar to those seen in women with PCOS. We used an untargeted nuclear magnetic resonance (NMR)-based metabolomics approach to understand the metabolic changes occurring in the plasma and kidney over time in female glucocorticoid-treated (GC-treated) mice. There are significant changes in plasma amino acid levels (valine, tyrosine, and proline) and their intermediates (2-hydroxybutyrate, 4-aminobutyrate, and taurine), whereas in kidneys, the TCA cycle metabolism (citrate, fumarate, and succinate) and the pentose phosphate (PP) pathway products (inosine and uracil) are significantly altered (p metabolic substrates in the plasma and kidneys of treated mice are associated with altered amino acid metabolism, increased cytoplasmic PP, and increased mitochondrial activity, leading to a more oxidized state. This study identifies biomarkers associated with metabolic dysfunction in kidney mitochondria of a prenatal gluococorticoid-treated mouse model of PCOS that may be used as early predictive biomarkers of oxidative stress in the PCOS metabolic disorder in women.

  2. Theoretical modeling of a self-referenced dual mode SPR sensor utilizing indium tin oxide film

    Science.gov (United States)

    Srivastava, Sachin K.; Verma, Roli; Gupta, Banshi D.

    2016-06-01

    A prism based dual mode SPR sensor was theoretically modeled to work as a self-referenced sensor in spectral interrogation scheme. Self-referenced sensing was achieved by sandwiching an indium tin oxide thin film in between the prism base and the metal layer. The proposed sensor possesses two plasmon modes similar to long and short range SPRs (LR- and SR-SPRs) and we have analogically used LRSPR and SRSPR for them. However, these modes do not possess usual long range character due to the losses introduced by the imaginary part of indium tin oxide (ITO) dielectric function. One of the two plasmon modes responds to change in analyte refractive index while the other remains fixed. The influence of various design parameters on the performance of the sensor was evaluated. The performance of the proposed sensor was compared, via control simulations, with established dual mode geometries utilizing silicon dioxide (SiO2), Teflon AF-1600 and Cytop. The design parameters of the established geometries were optimized to obtain self-referenced sensing operation. Trade-offs between the resonance spectral width, minimum reflectivity, shift in resonance wavelength and angle of incidence were examined for optimal design. The present study will be useful in the fabrication of self-referenced sensors where the ambient conditions are not quite stable.

  3. 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

  4. Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

    KAUST Repository

    Eldeeb, Mazen A.

    2016-08-30

    A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

  5. 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.

  6. 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

  7. 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.

  8. An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

    Science.gov (United States)

    Riedel, T. P.; Wolfe, G. M.; Danas, K. T.; Gilman, J. B.; Kuster, W. C.; Bon, D. M.; Vlasenko, A.; Li, S.-M.; Williams, E. J.; Lerner, B. M.; Veres, P. R.; Roberts, J. M.; Holloway, J. S.; Lefer, B.; Brown, S. S.; Thornton, J. A.

    2014-04-01

    Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm-3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable

  9. 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.

  10. An atomic charge model for graphene oxide for exploring its bioadhesive properties in explicit water.

    Science.gov (United States)

    Stauffer, D; Dragneva, N; Floriano, W B; Mawhinney, R C; Fanchini, G; French, S; Rubel, O

    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.

  11. Micromechanical Modeling of Solid Oxide Fuel Cell Anode Supports based on Three-dimensional Reconstructions

    DEFF Research Database (Denmark)

    Kwok, Kawai; Jørgensen, Peter Stanley; Frandsen, Henrik Lund

    2014-01-01

    The efficiency and lifetime of solid oxide fuel cells (SOFCs) is compromised by mechanical failure of cells in the system. Improving the mechanical reliability is a major step in ensuring feasibility of the technology. To quantify the stress in a cell, mechanical properties of the different layers...... need to be accurately known. Since the mechanical properties are heavily dependent on the microstructures of the materials, it is highly advantageous to understand the impact of microstructures and to be able to determine accurate effective mechanical properties for cell or stack scale analyses...... are computed by the finite element method. The macroscopic creep response of the porous anode support is determined based on homogenization theory. It is shown that micromechanical modeling provides an effective tool to study the effect of microstructures on the macroscopic properties....

  12. 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.

  13. 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.

  14. 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.

  15. Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

    Directory of Open Access Journals (Sweden)

    Schaller Melinda S

    2008-09-01

    Full Text Available Abstract Background The application of surface complexation models (SCMs to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO, pure kaolinite (from two sources and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples.

  16. 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

  17. Large scale computational chemistry modeling of the oxidation of highly oriented pyrolytic graphite.

    Science.gov (United States)

    Poovathingal, Savio; Schwartzentruber, Thomas E; Srinivasan, Sriram Goverapet; van Duin, Adri C T

    2013-04-04

    Large scale molecular dynamics (MD) simulations are performed to study the oxidation of highly oriented pyrolytic graphite (HOPG) by hyperthermal atomic oxygen beam (5 eV). Simulations are performed using the ReaxFF classical reactive force field. We present here additional evidence that this method accurately reproduces ab initio derived energies relevant to HOPG oxidation. HOPG is modeled as multilayer graphene and etch-pit formation and evolution is directly simulated through a large number of sequential atomic oxygen collisions. The simulations predict that an oxygen coverage is first established that acts as a precursor to carbon-removal reactions, which ultimately etch wide but shallow pits, as observed in experiments. In quantitative agreement with experiment, the simulations predict the most abundant product species to be O2 (via recombination reactions), followed by CO2, with CO as the least abundant product species. Although recombination occurs all over the graphene sheet, the carbon-removal reactions occur only about the edges of the etch pit. Through isolated defect analysis on small graphene models as well as trajectory analysis performed directly on the predicted etch pit, the activation energies for the dominant reaction mechanisms leading to O2, CO2, and CO product species are determined to be 0.3, 0.52, and 0.67 eV, respectively. Overall, the qualitative and quantitative agreement between MD simulation and experiment is very promising. Thus, the MD simulation approach and C/H/O ReaxFF parametrization may be useful for simulating high-temperature gas interactions with graphitic materials where the microstructure is more complex than HOPG.

  18. 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.

  19. 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.

  20. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  1. Glyoxal as a tracer of VOC oxidation chemistry: Comparison of measurements with model results for Blodgett Forest, California

    Science.gov (United States)

    Huisman, Andrew; Carlton, Annmarie; Keutsch, Frank

    2010-05-01

    We present a study investigating Volatile Organic Compound (VOC) oxidation chemistry in the context of regional ozone (O3) production during the BEARPEX 2007 and 2009 campaigns at Blodgett Forest Research Station (BFRS) in the Sierra Nevada mountains, CA. Measurements are compared with results from a regional model (US EPA CMAQ) and a zero dimensional (0-D) box model based on the Master Chemical Mechanism (MCM). We use glyoxal (CHOCHO) and formaldehyde (HCHO) as tracers for generalized oxidation processes and employ ratios of compounds (e.g. CHOCHO / HCHO, CHOCHO / MPAN) to study plume evolution as doing so attenuates the influence of meteorology. One of the goals of this study is to investigate the utility of glyoxal as a tracer of VOC oxidation chemistry for measurement/model comparisons, for which formaldehyde has served in the past. In this context, we investigate the discrepancies between models and measurements, and the degree to which these can be attributed to the representation of glyoxal chemistry (e.g. yields) or whether these discrepancies reflect VOC-HOx-NOx oxidation more generally, which has implications for ozone and secondary organic aerosol formation. Model results from CMAQ and the 0-D box model substantially overestimate the absolute measured concentration of CHOCHO at BFRS, and the CMAQ model also shows poor agreement with the diurnal profile. The 0-D box model also overestimates CHOCHO in data taken at the Caltech Indoor Air Chambers, suggesting that 2nd- and/or higher-generation yields of CHOCHO from isoprene are substantially overestimated in the MCM. 0-D model results that use attenuated 2nd- and higher-generation production of CHOCHO from isoprene show enhanced agreement with chamber results. We will present model results of the 0-D Box Model from BFRS employing these reduced yields that show improved agreement with measurements and also compare these results with the other models. We also present results obtained with two modifications of

  2. 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.

    2015-01-01

    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

  3. 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.

  4. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    Science.gov (United States)

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan; Xu, Donghai

    2017-03-01

    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process.

  5. 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.

  6. A Theoretical Solid Oxide Fuel Cell Model for Systems Controls and Stability Design

    Science.gov (United States)

    Kopasakis, George; Brinson, Thomas; Credle, Sydni

    2008-01-01

    As the aviation industry moves toward higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The hybrid solid oxide fuel cell system combines the fuel cell with a micro-turbine to obtain up to 70% cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multidiscipline system and the design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and a distribution system, and the fuel cell and micro-turbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. The novelty in this paper is that, first, the case is made why a high fidelity fuel cell mode is needed for systems control and stability designs. Second, a novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.

  7. Quantitative assessment of uncertainties for a model of tropospheric ethene oxidation using the European Photoreactor (EUPHORE)

    Science.gov (United States)

    Zádor, Judit; Wagner, Volker; Wirtz, Klaus; Pilling, Michael J.

    Methods of uncertainty analysis were used for comparison of the Master Chemical Mechanism version 3 (MCMv3) with measurements made in the European Photoreactor (EUPHORE) at Valencia (Spain) to investigate model-measurement discrepancies and to obtain information on the importance of wall effects. Two EUPHORE smog chamber measurements of ethene oxidation, under high and low NO x conditions were analysed by the following methods: (i) local uncertainty analysis, (ii) the global screening method of Morris and (iii) Monte Carlo (MC) analysis with Latin hypercube sampling. For both experiments, ozone (by 25% and 30%, respectively) and formaldehyde (by 34% and 40%, respectively) are significantly over-predicted by the model calculations, while the disagreement for other species is less substantial. According to the local uncertainty analysis and the Morris method, the most important contributor to ozone uncertainty under low NO x conditions is HOCH 2CH 2O 2+NO→HOCH 2CH 2O+NO 2, while under high NO x conditions OH+NO 2→HNO 3 is the main contributor. The MC simulations give an estimate of the 2σ uncertainty for ozone as ˜20% in both scenarios at the end of the experiment. The results suggest systematic disagreement between measurements and model calculations, although the origin of this is not clear. It seems that chamber effects alone are not responsible for the observed discrepancies.

  8. Numerical modeling of oxides of nitrogen based on density of biodiesel fuels

    Directory of Open Access Journals (Sweden)

    A. Gopinath, Sukumar Puhan, G. Nagarajan

    2010-03-01

    Full Text Available Biodiesel is an alternative fuel derived from vegetable oils or animal fats. Research has shown that biodiesel fueled engines produce lesser carbon monoxide, unburned hydrocarbon, and particulate emissions compared to mineral based diesel fuel but emit higher oxides of nitrogen (NOx emissions. NOx could be strongly correlated with density or cetane number of a fuel. The objective of the present work is to predict the NOx concentration of a neat biodiesel fueled compression ignition engine from the density of biodiesel fuels using regression model. Experiments were conducted at different engine loads and the results were given as inputs to develop the regression model. A single cylinder, four stroke, constant speed, air cooled, direct injection diesel engine was used for the experiments. Five different biodiesel fuels were used and NOx were measured at different engine loads. The NOx concentration was taken as response (dependent variable and the density values were taken as explanatory (independent variables. The regression model has yielded R2 values between 0.918 and 0.995. The maximum prediction error was found to be 3.01 %.

  9. Lithium perchlorate ion pairing in a model of amorphous polyethylene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J.W.; Duan, Y. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Curtiss, L.A.; Baboul, A.G. [Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    1999-08-01

    We report a molecular dynamics study of pairing and dynamics of lithium cation and perchlorate anion in a previously reported model of amorphous polyethylene oxide. We are particularly interested in the question of whether these ions pair in the model, as previously reported experimentally. We calculate the potential of mean force between a lithium and perchlorate ion in the system for several temperatures when a pair of ions is at various separation distances in our model. We find evidence for two minima in the potential of mean force, one at lithium{endash}chlorine separations of 3.5 {Angstrom} and about 6.5 {Angstrom}. We studied the same system with five ion pairs in the system and again find two minima at the same separation distances but in this case there is evidence of entropic effects in the binding free energy of the pairs at 3.5 {Angstrom}. A study of radial distribution functions permits us to deduce information concerning the structure of the paired states. {copyright} {ital 1999 American Institute of Physics.}

  10. A two-dimensional modeling of solid oxide fuel cell button cells with detailed electrochemistry mechanism

    Science.gov (United States)

    Li, Jingde; Bai, Zhengyu; Croiset, Eric

    2016-11-01

    A two-dimensional model of nickel/yttria-stabilized zirconia (Ni/YSZ) solid oxide fuel cell (SOFC) was developed for a button cell system. The model integrates the detailed catalytic, electrochemical elementary reactions with ionic/electronic conduction and multiple gas transport processes in SOFC. The model is validated using published experimental data for H2-H2O fuel gas under different cell sizes and operating conditions. The distributions of gas/surface phase species concentration and current density were predicted and the effects of operating temperature, fuel gas composition and fuel channel tube design on the cell performance were studied. The results show that the electrochemical reaction processes occurs mainly within a 20 μm distance from the anode/electrolyte interface and that the Ni catalyst surface is covered mainly by H(s). For the chamber channel design, the calculations show that the tube chamber should have a diameter no smaller than the cathode electrode to obtain the best SOFC performance.

  11. Extractive oxidative desulfurization of model oil/crude oil using KSF montmorillonite-supported 12-tungstophosphoric acid

    Directory of Open Access Journals (Sweden)

    Ezzat Rafiee

    2016-10-01

    Full Text Available Abstract 12-Tungstophosphoric acid (PW supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization (ODS of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide (H2O2 as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-to-sulfur compounds (S-compounds molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene (DBT and mixed thiophenic model oil under atmospheric pressure at 75 °C in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.

  12. Global sensitivity analysis of the GEOS-Chem chemical transport model: ozone and hydrogen oxides during ARCTAS (2008)

    Science.gov (United States)

    Christian, Kenneth E.; Brune, William H.; Mao, Jingqiu

    2017-03-01

    Developing predictive capability for future atmospheric oxidation capacity requires a detailed analysis of model uncertainties and sensitivity of the modeled oxidation capacity to model input variables. Using oxidant mixing ratios modeled by the GEOS-Chem chemical transport model and measured on the NASA DC-8 aircraft, uncertainty and global sensitivity analyses were performed on the GEOS-Chem chemical transport model for the modeled oxidants hydroxyl (OH), hydroperoxyl (HO2), and ozone (O3). The sensitivity of modeled OH, HO2, and ozone to model inputs perturbed simultaneously within their respective uncertainties were found for the flight tracks of NASA's Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) A and B campaigns (2008) in the North American Arctic. For the spring deployment (ARCTAS-A), ozone was most sensitive to the photolysis rate of NO2, the NO2 + OH reaction rate, and various emissions, including methyl bromoform (CHBr3). OH and HO2 were overwhelmingly sensitive to aerosol particle uptake of HO2 with this one factor contributing upwards of 75 % of the uncertainty in HO2. For the summer deployment (ARCTAS-B), ozone was most sensitive to emission factors, such as soil NOx and isoprene. OH and HO2 were most sensitive to biomass emissions and aerosol particle uptake of HO2. With modeled HO2 showing a factor of 2 underestimation compared to measurements in the lowest 2 km of the troposphere, lower uptake rates (γHO2 < 0. 055), regardless of whether or not the product of the uptake is H2O or H2O2, produced better agreement between modeled and measured HO2.

  13. Understanding DNA Under Oxidative Stress and Sensitization: The Role of Molecular Modeling

    Directory of Open Access Journals (Sweden)

    Antonio eMonari

    2015-07-01

    Full Text Available DNA is constantly exposed to damaging threats coming from oxidative stress, i.e. from the presence of free radicals and reactive oxygen species. Sensitization from exogenous and endogenous compounds that strongly enhance the frequency of light-induced lesions also plays an important role. The experimental determination of DNA lesions, though a difficult subject, is somehow well established and allows to elucidate even extremely rare DNA lesions. In parallel, molecular modeling has become fundamental to clearly understand the fine mechanisms related to DNA defects induction. Indeed, it offers an unprecedented possibility to get access to an atomistic or even electronic resolution. Ab initio molecular dynamics may also describe the time-evolution of the molecular system and its reactivity. Yet the modeling of DNA (photo-reactions does necessitate elaborate multi-scale methodologies to tackle a damage induction reactivity that takes place in a complex environment. The double-stranded DNA environment is first characterized by a very high flexibility, that dynamical effects are to be taken into account, but also a strongly inhomogeneous electrostatic embedding. Additionally, one aims at capturing more subtle effects, such as the sequence selectivity which is of critical important for DNA damage. The structure and dynamics of the DNA/sensitizers complexes, as well as the photo-induced electron- and energy-transfer phenomena taking place upon sensitization, should be carefully modeled. Finally the factors inducing different repair ratios for different lesions should also be rationalized.In this review we will critically analyze the different computational strategies used to model DNA lesions. A clear picture of the complex interplay between reactivity and structural factors will be sketched. The use of proper multi-scale modeling leads to the in-depth comprehension of DNA lesions mechanism and also to the rational design of new chemo-therapeutic agents.

  14. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2008-07-01

    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 more

  15. Anti-oxidative and anti-inflammatory effects of spirulina on rat model of non-alcoholic steatohepatitis

    Science.gov (United States)

    Pak, Wing; Takayama, Fusako; Mine, Manaka; Nakamoto, Kazuo; Kodo, Yasumasa; Mankura, Mitsumasa; Egashira, Toru; Kawasaki, Hiromu; Mori, Akitane

    2012-01-01

    The pathogenesis of nonalcoholic steatohepatitis (NASH) remains unclear, but accumulating data suggest oxidative stress and the relationship between inflammation and immunity plays a crucial role. The aim of this study is to investigate the spirulina, which is a blue-green algae rich in proteins and other nutritional elements, and its component-phycocyanin effect on a rat model of NASH. NASH model rats were established by feeding male Wistar rats with choline-deficient high-fat diet (CDHF) and intermittent hypoxemia by sodium nitrite challenge after 5 weeks of CDHF. After experimental period of 10 weeks, blood and liver were collected to determine oxidative stress injuries and efficacies of spirulina or phycocyanin on NASH model rats. In the NASH model rats, increase in plasma liver enzymes and liver fibrosis, increases in productions of reactive oxygen species from liver mitochondria and from leukocytes, the activation of nuclear factor-kappa B, and the change in the lymphocyte surface antigen ratio (CD4+/CD8+) were observed. The spirulina and phycocyanin administration significantly abated these changes. The spirulina or phycocyanin administration to model rats of NASH might lessen the inflammatory response through anti-oxidative and anti-inflammatory mechanisms, breaking the crosstalk between oxidative stress and inflammation, and effectively inhibit NASH progression. PMID:23170052

  16. Hepatocyte cytotoxicity induced by hydroperoxide (oxidative stress model) or glyoxal (carbonylation model): prevention by bioactive nut extracts or catechins.

    Science.gov (United States)

    Banach, Monica S; Dong, Qiang; O'Brien, Peter J

    2009-03-16

    Carbonyl and oxidative stress play important roles in the development of diabetic complications and have been shown to be augmented by various natural compounds and pharmacological agents. Nuts are a rich source of bioactive compounds and antioxidants and various beneficial health effects of nuts have been reported. This study was conducted to evaluate the cytoprotectiveness of various nut extracts and bioactive compounds found in nuts for decreasing cytotoxicity, lipid peroxidation and protein carbonylation in cell toxicity models of diabetes-related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, ethyl acetate or water were used to prepare crude hazelnut and walnut extracts, which were then used to screen for in vitro cytoprotection of freshly isolated rat hepatocytes against these toxins. The order of protection by nut extracts against hydroperoxide induced cell death was: walnut methanolic extract>walnut aqueous extract>lipophilic walnut extract>hazelnut aqueous extract>hazelnut methanolic extract whereas the lipophilic hazelnut extract did not protect against cell death. The order of protection against lipid peroxidation was the same except for the hazelnut methanolic extract, which prevented lipid peroxidation better than the hazelnut aqueous extract. Catechin, epicatechin and epigallocatechin gallate (EGCG) were investigated for possible protective effects against carbonyl stress cell death and protein carbonylation in hepatocytes. Catechin protected against glyoxal induced cell death and protein carbonylation, and even elicited protection when added to hepatocytes 30 min after the addition of glyoxal. When catechin and epicatechin were compared for protectiveness against glyoxal induced carbonyl stress in hepatocytes, epicatechin protected more effectively than catechin against cell death and protein carbonylation at 120 min. Both compounds also elicited better protection when premixed with glyoxal before addition to hepatocytes, compared

  17. Modeling aerosol surface chemistry and gas-particle interaction kinetics with K2-SURF: PAH oxidation

    Science.gov (United States)

    Shiraiwa, M.; Garland, R.; Pöschl, U.

    2009-04-01

    Atmospheric aerosols are ubiquitous in the atmosphere. They have the ability to impact cloud properties, radiative balance and provide surfaces for heterogeneous reactions. The uptake of gaseous species on aerosol surfaces impacts both the aerosol particles and the atmospheric budget of trace gases. These subsequent changes to the aerosol can in turn impact the aerosol chemical and physical properties. However, this uptake, as well as the impact on the aerosol, is not fully understood. This uncertainty is due not only to limited measurement data, but also a dearth of comprehensive and applicable modeling formalizations used for the analysis, interpretation and description of these heterogeneous processes. Without a common model framework, comparing and extrapolating experimental data is difficult. In this study, a novel kinetic surface model (K2-SURF) [Ammann & Pöschl, 2007; Pöschl et al., 2007] was used to describe the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs). Integrated into this consistent and universally applicable kinetic and thermodynamic process model are the concepts, terminologies and mathematical formalizations essential to the description of atmospherically relevant physicochemical processes involving organic and mixed organic-inorganic aerosols. Within this process model framework, a detailed master mechanism, simplified mechanism and parameterizations of atmospheric aerosol chemistry are being developed and integrated in analogy to existing mechanisms and parameterizations of atmospheric gas-phase chemistry. One of the key aspects to this model is the defining of a clear distinction between various layers of the particle and surrounding gas phase. The processes occurring at each layer can be fully described using known fluxes and kinetic parameters. Using this system there is a clear separation of gas phase, gas-surface and surface bulk transport and reactions. The partitioning of compounds can be calculated using the flux

  18. A predictive model of iron oxide nanoparticles flocculation tuning Z-potential in aqueous environment for biological application

    Energy Technology Data Exchange (ETDEWEB)

    Baldassarre, Francesca, E-mail: francesca.baldassarre@unisalento.it [University of Salento, Department of Cultural Heritage (Italy); Cacciola, Matteo, E-mail: matteo.cacciola@unirc.it [University “Mediterranea” of Reggio Calabria, DICEAM (Italy); Ciccarella, Giuseppe, E-mail: giuseppe.ciccarella@unisalento.it [University of Salento, Department of Innovation Engineering (Italy)

    2015-09-15

    Iron oxide nanoparticles are the most used magnetic nanoparticles in biomedical and biotechnological field because of their nontoxicity respect to the other metals. The investigation of iron oxide nanoparticles behaviour in aqueous environment is important for the biological applications in terms of polydispersity, mobility, cellular uptake and response to the external magnetic field. Iron oxide nanoparticles tend to agglomerate in aqueous solutions; thus, the stabilisation and aggregation could be modified tuning the colloids physical proprieties. Surfactants or polymers are often used to avoid agglomeration and increase nanoparticles stability. We have modelled and synthesised iron oxide nanoparticles through a co-precipitation method, in order to study the influence of surfactants and coatings on the aggregation state. Thus, we compared experimental results to simulation model data. The change of Z-potential and the clusters size were determined by Dynamic Light Scattering. We developed a suitable numerical model to predict the flocculation. The effects of Volume Mean Diameter and fractal dimension were explored in the model. We obtained the trend of these parameters tuning the Z-potential. These curves matched with the experimental results and confirmed the goodness of the model. Subsequently, we exploited the model to study the influence of nanoparticles aggregation and stability by Z-potential and external magnetic field. The highest Z-potential is reached up with a small external magnetic influence, a small aggregation and then a high suspension stability. Thus, we obtained a predictive model of Iron oxide nanoparticles flocculation that will be exploited for the nanoparticles engineering and experimental setup of bioassays.

  19. 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.

  20. Vanillin Attenuated Behavioural Impairments, Neurochemical Deficts, Oxidative Stress and Apoptosis Against Rotenone Induced Rat Model of Parkinson's Disease.

    Science.gov (United States)

    Dhanalakshmi, Chinnasamy; Janakiraman, Udaiyappan; Manivasagam, Thamilarasan; Justin Thenmozhi, Arokiasamy; Essa, Musthafa Mohamed; Kalandar, Ameer; Khan, Mohammed Abdul Sattar; Guillemin, Gilles J

    2016-08-01

    Vanillin (4-hydroxy-3-methoxybenzaldehyde), a pleasant smelling organic aromatic compound, is widely used as a flavoring additive in food, beverage, cosmetic and drug industries. It is reported to cross the blood brain barrier and also displayed antioxidant and neuroprotective activities. We previously reported the neuroprotective effect of vanillin against rotenone induced in in vitro model of PD. The present experiment was aimed to analyze the neuroprotective effect of vanillin on the motor and non-motor deficits, neurochemical variables, oxidative, anti-oxidative indices and the expression of apoptotic markers against rotenone induced rat model of Parkinson's disease (PD). Rotenone treatment exhibited motor and non-motor impairments, neurochemical deficits, oxidative stress and apoptosis, whereas oral administration of vanillin attenuated the above-said indices. However further studies are needed to explore the mitochondrial protective and anti-inflammatory properties of vanillin, as these processes play a vital role in the cause and progression of PD.

  1. Sperm Oxidative Stress Is Detrimental to Embryo Development: A Dose-Dependent Study Model and a New and More Sensitive Oxidative Status Evaluation

    Directory of Open Access Journals (Sweden)

    Letícia S. de Castro

    2016-01-01

    Full Text Available Our study aimed to assess the impact of sperm oxidative stress on embryo development by means of a dose-dependent model. In experiment 1, straws from five bulls were subjected to incubation with increasing H2O2 doses (0, 12.5, 25, and 50 μM. Motility parameters were evaluated by Computed Assisted System Analysis (CASA. Experiment 2 was designed to study a high (50 μM and low dose (12.5 μM of H2O2 compared to a control (0 μM. Samples were incubated and further used for in vitro fertilization. Analyses of motility (CASA, oxidative status (CellROX green and 2’-7’ dichlorofluorescein diacetate, mitochondrial potential (JC-1, chromatin integrity (AO, and sperm capacitation status (chlortetracycline were performed. Embryos were evaluated based on fast cleavage (30 h.p.i., cleavage (D=3, development (D=5, and blastocyst rates (D=8. We observed a dose-dependent deleterious effect of H2O2 on motility and increase on the percentages of positive cells for CellROX green, capacitated sperm, and AO. A decrease on cleavage and blastocyst rates was observed as H2O2 increased. Also, we detected a blockage on embryo development. We concluded that sperm when exposed to oxidative environment presents impaired motility traits, prooxidative status, and premature capacitation; such alterations resulting in embryo development fail.

  2. A deposit model for magmatic iron-titanium-oxide deposits related to Proterozoic massif anorthosite plutonic suites: Chapter K in Mineral Deposit Models for Resource Assessment

    Science.gov (United States)

    Woodruff, Laurel G.; Nicholson, Suzanne W.; Fey, David L.

    2013-01-01

    This descriptive model for magmatic iron-titanium-oxide (Fe-Ti-oxide) deposits hosted by Proterozoic age massif-type anorthosite and related rock types presents their geological, mineralogical, geochemical, and geoenvironmental attributes. Although these Proterozoic rocks are found worldwide, the majority of known deposits are found within exposed rocks of the Grenville Province, stretching from southwestern United States through eastern Canada; its extension into Norway is termed the Rogaland Anorthosite Province. This type of Fe-Ti-oxide deposit dominated by ilmenite rarely contains more than 300 million tons of ore, with between 10- to 45-percent titanium dioxide (TiO2), 32- to 45-percent iron oxide (FeO), and less than 0.2-percent vanadium (V).

  3. Hyperlipidemia affects neuronal nitric oxide synthase expression in brains of focal cerebral ischemia rat model

    Institute of Scientific and Technical Information of China (English)

    Jianji Pei; Liqiang Liu; Jinping Pang; Xiaohong Tian

    2008-01-01

    BACKGROUND: Hyperlipidemia, a risk factor for ischemic cerebrovascular disease, may mediate production of neuronal nitric oxide synthase (nNOS) to induce increased nitric oxide levels, resulting in brain neuronal injury. OBJECTIVE: To investigate effects of hyperlipidemia on brain nNOS expression, and to verify changes in infarct volume and pathology during reperfusion, as well as neuronal injury following ischemia/reperfusion in a rat model of focal cerebral ischemia. DESIGN, TIME AND SETTING: Complete, randomized grouping experiment was performed at the Laboratory of Physiology, Shanxi Medical University from March 2005 to March 2006. MATERIALS: A total of 144 eight-week-old, male, Wistar rats, weighing 160-180 g, were selected. A rat model of middle cerebral artery occlusion was established by suture method after 4 weeks of formulated diet. Nitric oxide kit and rabbit anti-rat nNOS kit were respectively purchased from Nanjing Jiancheng Bioengineering Institute, China and Wuhan Boster Biological Technology, Ltd., China. METHODS: The rats were equally and randomly divided into high-fat diet and a normal diet groups. Rats in the high-fat diet group were fed a high-fat diet, consisting of 10% egg yolk powder, 5% pork fat, and 0.5% pig bile salt combined with standard chow to create hyperlipidemia. Rats in the normal diet group were fed a standard rat chow. A total of 72 rats in both groups were randomly divided into 6 subgroups: sham-operated, 4-hour ischemia, 4-hour ischemia/2-hour reperfusion, 4-hour ischemia/4-hour reperfusion, 4-hour ischemia/6-hour reperfusion, and 4-hour ischemia/12-hour reperfusion, with 12 rats in each subgroup. MAIN OUTCOME MEASURES: nNOS expression was measured by immunohistochemistry, and pathomorphology changes were detected by hematoxylin-eosin staining. Infarct volume and nitric oxide levels were respectively measured using 2, 3, 5-triphenyltetrazolium chloride (TTC) and immunohistochemistry. RESULTS: In the ischemic region, pathology

  4. Carnitine Deficiency and Oxidative Stress Provoke Cardiotoxicity in an Ifosfamide-Induced Fanconi Syndrome Rat Model

    Directory of Open Access Journals (Sweden)

    Mohamed M. Sayed-Ahmed

    2010-01-01

    Full Text Available In addition to hemorrhagic cystitis, Fanconi Syndrome is a serious clinical side effect during ifosfamide (IFO therapy. Fanconi syndrome is a generalized dysfunction of the proximal tubule which is characterized by excessive urinary excretion of glucose, phosphate, bicarbonate, amino acids and other solutes excreted by this segment of the nephron including L-carnitine. Carnitine is essential cofactor for β-oxidation of long-chain fatty acids in the myocardium. IFO therapy is associated with increased urinary carnitine excretion with subsequent secondary deficiency of the molecule. Cardiac abnormalities in IFO-treated cancer patients were reported as isolated clinical cases. This study examined whether carnitine deficiency and oxidative stress, secondary to Fanconi Syndrome, provoke IFO-induced cardiomyopathy as well as exploring if carnitine supplementation using Propionyl-L-carnitine (PLC could offer protection against this toxicity. In the current study, an animal model of carnitine deficiency was developed in rats by D-carnitine-mildronate treatment Adult male Wistar albino rats were assigned to one of six treatment groups: the first three groups were injected intraperitoneally with normal saline, D-carnitine (DC, 250 mg/kg/day combined with mildronate (MD, 200 mg/kg/day and PLC (250 mg/kg/day, respectively, for 10 successive days. The 4th, 5th and 6th groups were injected with the same doses of normal saline, DC-MD and PLC, respectively for 5 successive days before and 5 days concomitant with IFO (50 mg/kg/day. IFO significantly increased serum creatinine, blood urea nitrogen (BUN, urinary carnitine excretion and clearance, creatine phosphokinase isoenzyme (CK-MB, lactate dehydrogenase (LDH, intramitochondrial acetyl-CoA/CoA-SH and thiobarbituric acid reactive substances (TBARS in cardiac tissues and significantly decreased adenosine triphosphate (ATP and total carnitine and reduced glutathione (GSH content in cardiac tissues. In carnitine

  5. Endothelial nitric oxide synthase uncoupling and perivascular adipose oxidative stress and inflammation contribute to vascular dysfunction in a rodent model of metabolic syndrome.

    Science.gov (United States)

    Marchesi, Chiara; Ebrahimian, Talin; Angulo, Orlando; Paradis, Pierre; Schiffrin, Ernesto L

    2009-12-01

    The metabolic syndrome represents a constellation of cardiovascular risk factors that promote the development of cardiovascular disease. Oxidative stress is a mediator of endothelial dysfunction and vascular remodeling. We investigated vascular dysfunction in the metabolic syndrome and the oxidant mechanisms involved. New Zealand obese (NZO) mice with metabolic syndrome and New Zealand black control mice were studied. NZO mice showed insulin resistance and increased visceral fat and blood pressure compared with New Zealand black mice. Mesenteric resistance arteries from NZO mice exhibited increased media:lumen ratio and media cross-sectional area, demonstrating hypertrophic vascular remodeling. Endothelium-dependent relaxation to acetylcholine, assessed by pressurized myography, was impaired in NZO mice, not affected by N(G)-nitro-l-arginine methyl ester, inhibitor of endothelial NO synthase, and improved by the antioxidant Tempol, suggesting reduced NO bioavailability and increased oxidative stress. Dimer:monomer ratio of endothelial NO synthase was decreased in NZO mice compared with New Zealand black mice, suggesting endothelial NO synthase uncoupling. Furthermore, vascular superoxide and peroxynitrite production was increased, as well as adhesion molecule expression. Perivascular adipose tissue of NZO mice showed increased superoxide production and NADPH oxidase activity, as well as adipocyte hypertrophy, associated with inflammatory Mac-3-positive cell infiltration. Vasoconstriction to norepinephrine decreased in the presence of perivascular adipose tissue in New Zealand black mice but was unaffected by perivascular adipose tissue in NZO mice, suggesting loss of perivascular adipose tissue anticontractile properties. Our data suggest that this rodent model of metabolic syndrome is associated with perivascular adipose inflammation and oxidative stress, hypertrophic resistance artery remodeling, and endothelial dysfunction, the latter a result of decreased NO

  6. Iodine's impact on tropospheric oxidants: a global model study in GEOS-Chem

    Science.gov (United States)

    Sherwen, T.; Evans, M. J.; Carpenter, L. J.; Andrews, S. J.; Lidster, R. T.; Dix, B.; Koenig, T. K.; Sinreich, R.; Ortega, I.; Volkamer, R.; Saiz-Lopez, A.; Prados-Roman, C.; Mahajan, A. S.; Ordóñez, C.

    2016-02-01

    We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I2OX, X = 2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of ˜ +90 % with available surface observations in the marine boundary layer (outside of polar regions), and of ˜ +73 % within the free troposphere (350 hPa terms of global tropospheric IY burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O3 burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven OX loss rate1 (748 Tg OX yr-1) is due to photolysis of HOI (78 %), photolysis of OIO (21 %), and reaction between IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O3 concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I2OX (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine- and iodine-driven tropospheric O3 burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8 %). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models. 1 Here OX is defined as O3 + NO2 + 2NO3 + PAN + PMN+PPN + HNO4 + 3N2O5 + HNO3 + BrO + HOBr + BrNO2+2BrNO3 + MPN + IO + HOI + INO2 + 2INO3 + 2OIO+2I2O2 + 3I2O3 + 4I2O4, where PAN = peroxyacetyl nitrate, PPN = peroxypropionyl nitrate, MPN = methyl peroxy nitrate, and MPN

  7. Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

    Institute of Scientific and Technical Information of China (English)

    Ali Darvishi; Razieh Davand; Farhad Khorasheh; Moslem Fattahi

    2016-01-01

    An industrial scale propylene production via oxidative dehydrogenation of propane (ODHP) in multi-tubular re-actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of smal diameter tubes immersed in a shel through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefin over V2O5/γ-Al2O3 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa-rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100%conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run-away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl-ene production in an industrial scale reactor.

  8. Controlled Hydrogen Peroxide Decomposition for a Solid Oxide Fuel Cell (SOFC) Oxidant Source with a Microreactor Model

    Science.gov (United States)

    2007-10-01

    microchannel reactor for hydrogen peroxide decomposition is being developed for integration with fuel cell systems that can power undersea vehicles...the subunits of a microchemical reactor system. The basis of the present model is a microchannel reactor . The model description, governing equations...the 2007 COMSOL Users Conference Boston, 4-6 Oct, Newton. MA 14. ABSTRACT A microchannel reactor for hydrogen peroxide decomposition is being

  9. Anticonvulsant and proconvulsant roles of nitric oxide in experimental epilepsy models

    Directory of Open Access Journals (Sweden)

    Del-Bel E.A.

    1997-01-01

    Full Text Available The effect of acute (120 mg/kg and chronic (25 mg/kg, twice a day, for 4 days intraperitonial injection of the nitric oxide (NO synthase (NOS inhibitor NG-nitro-L-arginine (L-NOARG was evaluated on seizure induction by drugs such as pilocarpine and pentylenetetrazole (PTZ and by sound stimulation of audiogenic seizure-resistant (R and audiogenic seizure-susceptible (S rats. Seizures were elicited by a subconvulsant dose of pilocarpine (100 mg/kg only after NOS inhibition. NOS inhibition also simultaneously potentiated the severity of PTZ-induced limbic seizures (60 mg/kg and protected against PTZ-induced tonic seizures (80 mg/kg. The audiogenic seizure susceptibility of S or R rats did not change after similar treatments. In conclusion, proconvulsant effects of NOS inhibition are suggested to occur in the pilocarpine model and in the limbic components of PTZ-induced seizures, while an anticonvulsant role is suggested for the tonic seizures induced by higher doses of PTZ, revealing inhibitor-specific interactions with convulsant dose and also confirming the hypothesis that the effects of NOS inhibitors vary with the model of seizure

  10. Modelling of gaseous dimethylamine in the global atmosphere: impacts of oxidation and aerosol uptake

    Directory of Open Access Journals (Sweden)

    F. Yu

    2014-07-01

    Full Text Available Recent laboratory studies indicate that while a dimethylamine concentration ([DMA] of several pptv can substantially enhance nucleation rates, such an enhancement drops significantly as [DMA] decreases below a few pptv. Here we study global distributions of amines with a chemistry transport model. DMA's lifetime is quite short (1–2 h in some regions due to aerosol uptake and oxidation. Aerosol uptake is important over regions of high anthropogenic emissions, while the decrease of the uptake coefficient (γ from 0.03 to 0.001 in these regions increases the modeled amine concentrations by a factor of ~5. Further decrease of γ from 0.001 to 0 has a small (<10% effect on the predicted amine concentrations. With the estimated global emission flux, from the reference, our simulations indicate that [DMA] in the surface layer is generally less than 1 pptv over major continents and below 0.1 pptv over oceans, decreasing quickly with altitude. Total concentrations of methylamines are about one order of magnitude higher than that of DMA. A comparison of simulated and observed [DMA] shows that the values of the simulated [DMA] are close to the measured values for the various urban sites but are substantially lower (by 1–2 orders of magnitude than those measured at the rural, coastal, and marine sites.

  11. Modeling and optimization of catalytic partial oxidation methane reforming for fuel cells

    Science.gov (United States)

    Chaniotis, A. K.; Poulikakos, D.

    The objective of this paper is the investigation and optimization of a micro-reformer for a fuel cell unit based on catalytic partial oxidation using a systematic numerical study of chemical composition and inflow conditions. The optimization targets hydrogen production from methane. Additionally, the operating temperature, the amount of carbon formation and the methane conversion efficiency are taking into account. The fundamental investigation is first based on simplified reactor models (surface perfectly stirred reactor (SPRS)). A detailed surface chemistry mechanism is adopted in order to capture all the important features of the reforming process. As a consequence, the residence time of the process is taken into account, which means that the products are not necessary in equilibrium. Subsequently, in order to test the validity of the findings from the simplified reactor model, more detailed simulations (involving the Navier-Stokes equations) were performed for the regions of interest. A region where all the targeted operating conditions are satisfied and the yield of hydrogen is around 80% is identified.

  12. Role of Renin-Angiotensin System and Oxidative Stress on Vascular Inflammation in Insulin Resistence Model

    Directory of Open Access Journals (Sweden)

    N. F. Renna

    2013-01-01

    Full Text Available (1 This study aims to demonstrate the causal involvement of renin angiotensin system (RAS and oxidative stress (OS on vascular inflammation in an experimental model of metabolic syndrome (MS achieved by fructose administration to spontaneously hypertensive rats (FFHR during 12 weeks. (2 Chronic treatment with candesartan (C (10 mg/kg per day for the last 6 weeks or 4OH-Tempol (T (10−3 mmol/L in drinking water for the last 6 weeks reversed the increment in metabolic variables and systolic blood pressure. In addition, chronic C treatment reverted cardiovascular remodeling but not T. (3 Furthermore, chronic treatment with C was able to completely reverse the expression of NF-κB and VCAM-1, but T only reduced the expression. C reduced the expression of proatherogenic cytokines as CINC2, CINC3, VEGF, Leptin, TNF-alpha, and MCP-1 and also significantly reduced MIP-3, beta-NGF, and INF-gamma in vascular tissue in this experimental model. T was not able to substantially modify the expression of these cytokines. (4 The data suggest the involvement of RAS in the expression of inflammatory proteins at different vascular levels, allowing the creation of a microenvironment suitable for the creation, perpetuation, growth, and destabilization of vascular injury.

  13. Special quasirandom structure modeling of fluorite-structured oxide solid solutions with aliovalent cation substitutions

    Science.gov (United States)

    Wolff-Goodrich, Silas; Hanken, Benjamin E.; Solomon, Jonathan M.; Asta, Mark

    2015-07-01

    The accuracy of the special quasirandom structure (SQS) approach for modeling the structure and energetics of fluorite-structured oxide solid solutions with aliovalent cation substitutions is assessed in an ionic-pair potential study of urania and ceria based systems mixed with trivalent rare-earth ions. Mixing enthalpies for SQS supercells containing 96 and 324 lattice sites were calculated using ionic pair potentials for U0.5La0.5O1.75, U0.5Y0.5O1.75, Ce0.5La0.5O1.75, Ce0.5Y0.5O1.75, and Ce0.5Gd0.5O1.75, which all have stoichiometries of pyrochlores. The SQS results were compared to benchmark values for random substitutional disorder obtained using large supercell models. The calculations show significant improvement of the mixing enthalpy for the larger 324 site SQS, which is attributed to a better description of the structural distortions, as characterized by the radial distribution functions in relaxed systems.

  14. Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling.

    Science.gov (United States)

    Wu, Lei; Liu, Lin; Gao, Bin; Muñoz-Carpena, Rafael; Zhang, Ming; Chen, Hao; Zhou, Zuhao; Wang, Hao

    2013-12-10

    Although graphene oxide (GO) has been used in many applications to improve human life quality, its environmental fate and behavior are still largely unknown. In this work, a novel approach that combines experimental measurements and theoretical calculations was used to determine the aggregation kinetics of GO sheets in aqueous solutions under different chemistry conditions (e.g., cation valence and pH). Experimental data showed that both cation valence and pH showed significant effect on the aggregation of GO sheets. The measured critical coagulation concentrations were in good agreement with the predictions of the extended Schulze-Hardy rule. Ca(2+) and Mg(2+) were more effective than Na(+) in aggregating the GO sheets, which could be attributed to the cross-linking between GO sheets by the divalent cations through "bridging" the functional groups at the edges of the GO sheets. When solution pH increases, deprotonation of carboxylic groups was found to play a key role in increasing GO sheet stability and surface charge development. These results suggested that edge-to-edge and face-to-face interactions were the dominant modes of GO aggregation in the presence of divalent metal ions and H(+), respectively. A modified attachment efficiency (α) model was developed on the basis of the Maxwell approach with considerations of both primary and secondary minima. The model predictions matched the experimental measurements of the aggregation kinetics of GO sheets in aqueous solutions under all of the tested experimental conditions well.

  15. Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake.

    Science.gov (United States)

    Houle, F A; Hinsberg, W D; Wilson, K R

    2015-02-14

    An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

  16. Modeling of Proton-Conducting Solid Oxide Fuel Cells Fueled with Syngas

    Directory of Open Access Journals (Sweden)

    Meng Ni

    2014-07-01

    Full Text Available Solid oxide fuel cells (SOFCs with proton conducting electrolyte (H-SOFCs are promising power sources for stationary applications. Compared with other types of fuel cells, one distinct feature of SOFC is their fuel flexibility. In this study, a 2D model is developed to investigate the transport and reaction in an H-SOFC fueled with syngas, which can be produced from conventional natural gas or renewable biomass. The model fully considers the fluid flow, mass transfer, heat transfer and reactions in the H-SOFC. Parametric studies are conducted to examine the physical and chemical processes in H-SOFC with a focus on how the operating parameters affect the H-SOFC performance. It is found that the presence of CO dilutes the concentration of H2, thus decreasing the H-SOFC performance. With typical syngas fuel, adding H2O cannot enhance the performance of the H-SOFC, although water gas shift reaction can facilitate H2 production.

  17. Gaseous neurotransmitter nitric oxide: Its role in experimental models of epilepsy

    Directory of Open Access Journals (Sweden)

    Hrnčić D.

    2012-01-01

    Full Text Available Epilepsy is one of the leading neurological disorders and affects 1-2% of the world’s population. Generally, it is a result of an imbalance between excitatory and inhibitory phenomena in the central nervous system (CNS, but the mechanisms of its initiation and propagation still require further investigations. Experimental models represent one of the most powerful tools to better understand the mechanisms of epileptogenesis. Nitric oxide (NO is gaseous molecule with pleiotropic physiological and pathological effects in almost all organ systems and intriguing biological relevance, especially in the CNS where it acts as a gaseous neurotransmitter. The role of NO in the generation of epilepsy is highly contradictory, since there is evidence of its anticonvulsive, as well as proconvulsive properties. Therefore, we will discuss in this review the involvement of NO-mediated signaling pathways in the mechanisms of epileptogenesis, taking into account the findings revealed in experimental studies on animal models of epilepsy. [Acknowledgments. This study was supported by Ministry of Education and Science of Serbia, Grant No. 175032

  18. Effect of Centella asiatica on Oxidative Stress and Lipid Metabolism in Hyperlipidemic Animal Models

    Directory of Open Access Journals (Sweden)

    Yun Zhao

    2014-01-01

    Full Text Available Hyperlipidemia and many other metabolic diseases are related to oxidative stress. Centella asiatica is a traditional Chinese medicine whose antioxidant effect in vitro has been reported. We are interested in whether it possesses this effect in vivo and hence modulates lipid metabolism. Therefore, experiments were carried out on mice and golden hamsters regarding its antioxidant and hypolipidemic effect. We observed that a fraction (CAF3 of the ethanol extract (CAE of Centella asiatica had a cholesterol decrease of 79% and a triglyceride decrease of 95% in acute mice model, so CAF3 was further investigated in high-fat-fed hamster model. It was shown that CAF3 increased SOD and GSH-Px activities and decreased MDA level, and it also improved TC, TG, LDL-C, HDL-C, AST, and ALT levels. L-CAT and SR-BI gene expression in hamsters were increased. Taken together, our data suggest that the CAF3 fraction of Centella asiatica has antioxidant and hypolipidemic properties.

  19. Mechanistic modeling of vacuum UV advanced oxidation process in an annular photoreactor.

    Science.gov (United States)

    Crapulli, F; Santoro, D; Sasges, M R; Ray, A K

    2014-11-01

    A novel mechanistic model that describes the vacuum UV advanced oxidation process in an annular photoreactor initiated by 172 nm and 185 nm (in combination with 253.7 nm, with and without exogenous H2O2) is presented in this paper. The model was developed from first principles by incorporating the vacuum UV-AOP kinetics into the theoretical framework of in-series continuous flow stirred tank reactors. After conducting a sensitivity analysis, model predictions were compared against experiments conducted under a variety of conditions: (a) photo-induced formation of hydrogen peroxide by water photolysis at 172 nm (for both air- and oxygen-saturated conditions); (b) photo-induced formation of hydrogen peroxide by water photolysis at 185 + 253.7 nm (in the presence of formic acid, with and without the initial addition of hydrogen peroxide); (c) direct photolysis of hydrogen peroxide by 253.7 nm; (d) degradation of formic acid by 185 + 253.7 nm (with and without initial addition of hydrogen peroxide); and (e) degradation of formic acid by 253.7 nm (with the addition of exogenous hydrogen peroxide). In all cases, the model was able to accurately predict the time-dependent profiles of hydrogen peroxide and formic acid concentrations. Two newly recognized aspects associated with water photolysis were identified through the use of the validated model. Firstly, unlike the 185 nm and 253.7 nm cases, water photolysis by the 172 nm wavelength revealed a depth of photoactive water layer an order of magnitude greater (∼230-390 μm, depending on the specific operating conditions) than the 1-log photon penetration layer (∼18 μm). To further investigate this potentially very important finding, a computational fluid dynamics model was set up to assess the role of transport mechanisms and species distributions within the photoreactor annulus. The model confirmed that short-lived hydroxyl radicals were present at a radial distance far beyond the ∼18 μm photon

  20. Transient kinetic modeling of the ethylene and carbon monoxide oxidation over a commercial automotive exhaust gas catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Harmsen, J.M.A.; Hoebink, J.H.B.J.; Schouten, J.C.

    2000-03-01

    The transient kinetics of ethylene oxidation by oxygen over a commercial Pt/Rh/CeO{sub 2}/{gamma}-Al{sub 2}O{sub 3} three-way catalyst were modeled. Experiments were carried out in a fixed-bed microreactor with two separate inlets, enabling alternate feeding of ethylene and oxygen with frequencies up to {1/4} Hz. The experimental conditions resemble the cold-start period of an Otto engine in a car. Two types of adsorbed ethylene species seem to exist. A selective catalyst deactivation for oxygen adsorption, due to deposition of carbonaceous species, was found. A kinetic model was developed, based on elementary reaction steps, that allows one to describe the experiments quantitatively. Furthermore, this model was combined with the published model for transient carbon monoxide oxidation over the same catalyst, which enables one to predict the results of simultaneous ethylene and carbon monoxide oxidation. Both components react in rather distinct zones, with ethylene being converted only when carbon monoxide oxidation is almost complete.

  1. In situ spectroscopic investigation of the cobalt-catalyzed oxidation of lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2011-01-01

    The cobalt-catalyzed oxidation of lignin and lignin model compounds using molecular oxygen in ionic liquids proceeds readily under mild conditions, but mechanistic insight and evidence for the species involved in the catalytic cycle is lacking. In this study, a spectroscopic investigation of the com

  2. Agreement of central site measurements and land use regression modeled oxidative potential of PM2.5 with personal exposure

    NARCIS (Netherlands)

    Yang, Aileen; Hoek, Gerard; Montagne, Denise; Leseman, Daan L A C; Hellack, Bryan; Kuhlbusch, Thomas A J; Cassee, Flemming R; Brunekreef, Bert; Janssen, Nicole A H

    2015-01-01

    Oxidative potential (OP) of ambient particulate matter (PM) has been suggested as a health-relevant exposure metric. In order to use OP for exposure assessment, information is needed about how well central site OP measurements and modeled average OP at the home address reflect temporal and spatial v

  3. A blueberry enriched diet attenuates nephropathy in a rat model of hypertension via reduction in oxidative stress

    Science.gov (United States)

    Objective: To assess renoprotective effects of a blueberry-enriched diet in a rat model of hypertension. Background: Oxidative stress (OS) appears to be involved in the development of hypertension and related renal injury. Pharmacological antioxidants can attenuate hypertension and hypertension-indu...

  4. Experimental coupling and modelling of wet air oxidation and packed-bed biofilm reactor as an enhanced phenol removal technology.

    Science.gov (United States)

    Minière, Marine; Boutin, Olivier; Soric, Audrey

    2017-01-25

    Experimental coupling of wet air oxidation process and aerobic packed-bed biofilm reactor is presented. It has been tested on phenol as a model refractory compound. At 30 MPa and 250 °C, wet air oxidation batch experiments led to a phenol degradation of 97% and a total organic carbon removal of 84%. This total organic carbon was mainly due to acetic acid. To study the interest of coupling processes, wet air oxidation effluent was treated in a biological treatment process. This step was made up of two packed-bed biofilm reactors in series: the first one acclimated to phenol and the second one to acetic acid. After biological treatment, phenol and total organic carbon removal was 99 and 97% respectively. Thanks to parameters from literature, previous studies (kinetic and thermodynamic) and experimental data from this work (hydrodynamic parameters and biomass characteristics), both treatment steps were modelled. This modelling allows the simulation of the coupling process. Experimental results were finally well reproduced by the continuous coupled process model: relative error on phenol removal efficiency was 1 and 5.5% for wet air oxidation process and packed-bed biofilm reactor respectively.

  5. Caenorhabditis elegans: A Useful Model for Studying Metabolic Disorders in Which Oxidative Stress Is a Contributing Factor

    Science.gov (United States)

    Moreno-Arriola, Elizabeth; Cárdenas-Rodríguez, Noemí; Coballase-Urrutia, Elvia; Pedraza-Chaverri, José; Carmona-Aparicio, Liliana; Ortega-Cuellar, Daniel

    2014-01-01

    Caenorhabditis elegans is a powerful model organism that is invaluable for experimental research because it can be used to recapitulate most human diseases at either the metabolic or genomic level in vivo. This organism contains many key components related to metabolic and oxidative stress networks that could conceivably allow us to increase and integrate information to understand the causes and mechanisms of complex diseases. Oxidative stress is an etiological factor that influences numerous human diseases, including diabetes. C. elegans displays remarkably similar molecular bases and cellular pathways to those of mammals. Defects in the insulin/insulin-like growth factor-1 signaling pathway or increased ROS levels induce the conserved phase II detoxification response via the SKN-1 pathway to fight against oxidative stress. However, it is noteworthy that, aside from the detrimental effects of ROS, they have been proposed as second messengers that trigger the mitohormetic response to attenuate the adverse effects of oxidative stress. Herein, we briefly describe the importance of C. elegans as an experimental model system for studying metabolic disorders related to oxidative stress and the molecular mechanisms that underlie their pathophysiology. PMID:24955209

  6. Caenorhabditis elegans: A Useful Model for Studying Metabolic Disorders in Which Oxidative Stress Is a Contributing Factor

    Directory of Open Access Journals (Sweden)

    Elizabeth Moreno-Arriola

    2014-01-01

    Full Text Available Caenorhabditis elegans is a powerful model organism that is invaluable for experimental research because it can be used to recapitulate most human diseases at either the metabolic or genomic level in vivo. This organism contains many key components related to metabolic and oxidative stress networks that could conceivably allow us to increase and integrate information to understand the causes and mechanisms of complex diseases. Oxidative stress is an etiological factor that influences numerous human diseases, including diabetes. C. elegans displays remarkably similar molecular bases and cellular pathways to those of mammals. Defects in the insulin/insulin-like growth factor-1 signaling pathway or increased ROS levels induce the conserved phase II detoxification response via the SKN-1 pathway to fight against oxidative stress. However, it is noteworthy that, aside from the detrimental effects of ROS, they have been proposed as second messengers that trigger the mitohormetic response to attenuate the adverse effects of oxidative stress. Herein, we briefly describe the importance of C. elegans as an experimental model system for studying metabolic disorders related to oxidative stress and the molecular mechanisms that underlie their pathophysiology.

  7. Modelling and simulation of photocatalytic oxidation mechanism of chlorohalogenated substituted phenols in batch systems: Langmuir-Hinshelwood approach.

    Science.gov (United States)

    Khuzwayo, Z; Chirwa, E M N

    2015-12-30

    This study investigated, modelled and simulated the influence of multi-chlorohalogenation in heterogeneous photocatalytic degradation of substituted phenols (pentachlorophenol (PCP), trichlorophenol (TCP), dichlorophenol (DCP), and monochlorophenol (CP)). The Langmuir-Hinshelwood approach was applied to determine oxidation kinetics. Aquasim 2.0 computational software was used to model, simulate and estimate model parameters of the different chlorophenols. Chemical adsorption equilibrium isotherms for the four chlorophenols and phenol were studied and modelled for adsorption onto titanium dioxide (TiO2) semiconductor catalyst. Langmuir adsorption parameters were determined and used to calculate adsorption constant and maximum adsorption capacity. The adsorption of chloride phenolics onto titanium dioxide catalyst increased in the order of 4 - CP Photocatalytic studies analysed the efficiency of oxidation and found improved degradation with higher chloride substituted phenolics in the order of PCP > TCP > DCP ≥ 4 - CP. Photocatalytic parameters were calculated and estimated along with sensitivity and uncertainty analyses.

  8. Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Peyton, Brent M. [Montana State Univ., Bozeman, MT (United States); Timothy, Ginn R. [Univ. of California, Davis, CA (United States); Sani, Rajesh K. [South Dakota School of Mines and Technology, Rapid City, SD (United States)

    2013-08-14

    citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO2 reoxidation as Fe(III) oxidizes HS– preferentially over UO2. The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO2) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.

  9. Biogenic SOA formation through gas-phase oxidation and gas-to-particle partitioning – comparison between process models of varying complexity

    Directory of Open Access Journals (Sweden)

    E. Hermansson

    2014-05-01

    Full Text Available Biogenic volatile organic compounds (BVOCs emitted by the vegetation play an important role for the aerosol mass loadings since the oxidation products of these compounds can take part in the formation and growth of secondary organic aerosols (SOA. The concentrations and properties of BVOCs and their oxidation products in the atmosphere are poorly characterized, which leads to high uncertainties in modeled SOA mass and properties. In this study the formation of SOA has been modeled along an air mass trajectory over the northern European boreal forest using two aerosol dynamics box models where the prediction of the condensable organics from the gas-phase oxidation of BVOC is handled with schemes of varying complexity. The use of box model simulations along an air mass trajectory allows us to, under atmospheric relevant conditions, compare different model parameterizations and their effect on SOA formation. The result of the study shows that the modeled mass concentration of SOA is highly dependent on the organic oxidation scheme used to predict the oxidation products. A near-explicit treatment of organic gas-phase oxidation (Master Chemical Mechanism version 3.2 was compared to oxidation schemes that use the volatility basis set (VBS approach. The resulting SOA mass modeled with different VBS-schemes varies by a factor of about 7 depending on how the first generation oxidation products are parameterized and how they subsequently age (e.g. how fast the gas-phase oxidation products react with the OH-radical, how they respond to temperature changes and if they are allowed to fragment during the aging process. Since the VBS approach is frequently used in regional and global climate models due to its relatively simple treatment of the oxidation products compared to near-explicit oxidation schemes; better understanding of the abovementioned processes are needed. Compared to the most commonly used VBS-schemes, the near-explicit method produces less

  10. Mathematical Modeling Analysis and Optimization of Key Design Parameters of Proton-Conductive Solid Oxide Fuel Cells

    OpenAIRE

    Liu, Hong; Akhtar, Zoheb; Li, Peiwen; Wang, Kai

    2014-01-01

    A proton-conductive solid oxide fuel cell (H-SOFC) has the advantage of operating at higher temperatures than a PEM fuel cell, but at lower temperatures than a SOFC. This study proposes a mathematical model for an H-SOFC in order to simulate the performance and optimize the flow channel designs. The model analyzes the average mass transfer and species’ concentrations in flow channels, which allows the determination of an average concentration polarization in anode and cathode gas channels, th...

  11. Mathematical Modeling Analysis and Optimization of Key Design Parameters of Proton-Conductive Solid Oxide Fuel Cells

    OpenAIRE

    Hong Liu; Zoheb Akhtar; Peiwen Li; Kai Wang

    2014-01-01

    A proton-conductive solid oxide fuel cell (H-SOFC) has the advantage of operating at higher te