The oxidation of boron carbide in steam or air was recently extensively studied especially in Forschungszentrum Karlsruhe, Institut fuer Materialforschung. An important data set is available for the interaction modelling. An oxygen diffusion model through the superficial liquid boron oxide formed on the boron carbide external surface associated to a superficial reaction between the liquid boron oxide and steam is proposed to simulate the experimental kinetics from BOX rig and thermogravimetric tests on the interaction between steam and boron carbide at a temperature range 800 C to 1400 C. The oxygen diffusion model will be also useful to simulate interaction between boron carbide and Ar+O2 (air simulation) atmosphere when the steam pressure becomes zero. From the analysis of BOX rig experimental kinetics of non-condensable (H2, CO2, CO and CH4) gases we propose ...
This paper describes the effects of SiC coating on the oxidation resistance of C/C composites in combusting fields, which are expected to be applied to high temperature structural materials at over 1770K. The coating methods employed were CVD and pack cementation. The time changes in weight loss of the specimens were measured at temperatures of 1770K and 1900K under the equivalence ratio of 0.9 generated by methane-air combustion, and the surface of the specimens before and after the experiment was observed by SEM. Although the weight loss of the specimens coated by the CVD method was minimal, the coating layer was easily peeled off from the substrate. On the other hand, the layer of the specimens coated by the pack cementation method was stable and adhered to the substrate, but the substrate was degraded because of penetration of oxygen through the pores in the layer. To cover the pores, the specimens were additionally coated with glass materials comprised of ...
TaC and TaC-1wt.% B4C powders were consolidated using spark plasma sintering (SPS) at 1850^oC and varying pressure of 100, 255 and 363MPa. The effect of pressure on the densification and grain size is evaluated. The role of nano-sized B4C as sintering aid and grain growth inhibitor is studied by means of XRD, SEM and high resolution TEM. Fully dense TaC samples were produced at a pressure of 255MPa and higher at 1850^oC. The increasing pressure also resulted in an increase in TaC grain size. Addition of B4C leads to an increase in the density of 100MPa sample from 89% to 97%. B4C nano-powder resists grain growth even at high pressure of 363MPa. The formation of TaB2/Carbon at TaC grain boundaries helps in pinning the grain boundary and ...
The effects of Fe and B_4C on the sintering behavior and mechanical properties of TiB_2 ceramics have been studied. Sintering was performed in an Ar atmosphere at 2000 degrees C using attrition-milled TiB_2 powder. When a small amount of Fe (0.5 wt%) was added, abnormal grain growth occurred and the sintered density was low. In the case of B_4C added along with 0.5 wt% Fe, however, abnormal grain growth was remarkably suppressed, and the sintered density was increased up to 95% of theoretical. But with excess Fe addition (5 wt%), B_4C grains did not act as a grain growth inhibitor, and B_4C grains were frequently trapped in large TiB_2 grains. The best mechanical properties were obtained for the TiB_2-10 wt% ...
May 31, 2011 ... A Theoretical Solid Oxide Fuel Cell Model for System Controls and Stability Design AUTHOR(S): Kopasakis, George; Brinson, Thomas; Credle, ...
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 ...
Boron carbide is a high-technological ceramic material (it is used for lightweight armor, neutron absorbers, wear pieces, etc.). Hot pressing (2200"0C, 40 MPa, Ar atmosphere) and recently high isostatic pressing, are the best know ways for industrial preparation of boron carbide items. Pressureless sintering using metallic, inorganic, B+C, additives is not successful, since, despite having a high density, impurities remain present. Pressureless sintering of boron carbide (or silicon carbide composite) using free carbon addition, produced by in-situ pyrolysis of a Novolaque-type phenol-formaldehyde resin (#approx =# 9 wt%), is now possible in industry. A promising new method is the use of organic precursors, e.g. polycarbosilane with a small amount of phenolic resin, giving CSi and C by in-situ pyrolysis; the resulting boron carbide ceramics have high density (> 92%) and contain no free carbon and a small amount of SiC (#approx =# 5 wt%). The mechanical properties of sintered ...
The effect of sodium on the partial oxidation of methane over MoO{sub 3}-SiO{sub 2} in the presence of molecular oxygen has been investigated. As in the sodium-free case, the major products are formaldehyde, carbon monoxide, carbon dioxide, and water. Kinetic analysis indicates that methane is directly oxidized to formaldehyde and carbon dioxide. Formaldehyde is oxidized to carbon monoxide, which is itself further oxidized, providing an alternative route to carbon dioxide. The kinetic model shows that sodium poisons the direct oxidation of methane to formaldehyde and carbon dioxide, but promotes the oxidation of formaldehyde and carbon monoxide. Model predictions of rates and selectivities are in good agreement with the experimental data. A mechanism that explains both the poisoning and promotion effects of sodium on ...
Green River oil shale was air oxidized at subretorting temperatures. Off gases consisting of nitrogen, oxygen, carbon monoxide, carbon dioxide, and water were monitored and quantitatively determined. A mathematical model of the oxidation reactions based on a shrinking core model has been developed. This model incorporates the chemical reaction of oxygen and the organic material in the oil shale as well as the diffusivity of the oxygen into the shale particle. Diffusivity appears to be rate limiting for the oxidation. Arrhenius type equations, which include a term for oil shale grade, have been derived for both the chemical reaction and the diffusivity.
Reactive oxygen species (ROS), inevitable byproducts of aerobic metabolism, are known to cause oxidative damage to cells and molecules. This, in turn, is widely accepted as a pivotal determinant of...Full Text Available
It is shown analytically and experimentally that thermally stimulated current (TSC) measurements at negative bias incompletely describe oxide-trap charge in SIMOX and bipolar base oxides irradiated at 0 V. Positive-bias TSC is also required.
The construction materials used in coolant systems in nuclear power plants become covered with oxide films as a result of exposure to the aqueous environment. The susceptibility of the materials to different forms of corrosion, as well as the extent of the incorporation of radioactive species on the surfaces of the primary circuit, are greatly influenced by the physical and chemical properties of these oxide films. The composition and characteristics of the oxide films in turn depend on the applied water chemistry. This work was undertaken in order to collect and evaluate the present views on the structure and behaviour of oxide films formed on iron- and nickel-based materials in aqueous environments. This survey should serve to recognise the areas in which more understanding and research effort is needed. The review begins with a discussion on the bulk oxides of iron, nickel and ...
The chemiosmotic model of energy transduction offers a satisfying and widely confirmed understanding of the action of uncouplers on such processes as oxidative phosphorylation; the uncoupler, by facilitating...Full Text Available
Considering the status of knowledge on corrosion and corrosion protection and especially the need for long term compatibility data of structural materials in HLM a set of experiments to generate reliable long term data was defined and performed. The long term corrosion behaviour of the two structural materials foreseen in ADS, 316L and T91, was investigated in the design relevant temperature field, i.e. from 300 to 550degreeC. The operational window of the two steels in this temperature range was identified and all oxidation data were used to develop and validate the models of oxide scale growth in PbBi. A mechanistic model capable to predict the oxidation rate applying some experimentally fitted parameters has been developed. This model assumes parabolic oxidation and might be used for de...
A detection theory is developed for point-contact metal-oxide-metal (MOM) systems. A system with heterogeneous oxide strongly bonded to the substrate is considered. It is shown that the form of the functional connection between the barrier heights and the ultimate compressive strength of the oxide has no substantial influence on the voltage-current characteristics of the system. Quantitative analysis indicates that a MOM system can behave as a tunnel diode and as a diode with a Schottky barrier. The model permits the determination of the optimum construction of long-life detectors based on MOM point-contacts.-
With an objective to learn reactivity of coal at its surface, surfaces of oxidized coal samples were investigated. Miike coal was oxidized by using {sup 18}O2 in a closed loop system. As the reaction progresses, proportion of CO2 including isotopes increased rapidly as a result of oxidation of CO sites existing in the coal and the newly generated C{sup 18}O sites. The oxidizing reaction progressed via oxygen adsorbing sites generated near the surface, and oxygen containing groups. An FT-IR analysis estimated the depth of the oxidized layer to be 10{mu}m or less from particle surface. The oxidized coal was pulverized to see its surface condition. Functional groups introduced by the oxidation enter into the vicinity of the surface in a form to desorb as CO. CO2 is trapped in inner pores. The coal surface was observed by using an atomic force ...
Trichloroethylene (TCE) pharmacokinetics have been studied in experimental animals and humans for over 30 years. Compartmental and physiologically based pharmacokinetic (PBPK) models have been developed...Full Text Available
Calculations, drawing principally on developments at AERE Harwell, of the relaxation about lattice defects are reviewed with emphasis on the techniques required for such calculations. The principles of defect modelling are outlined and various programs developed for defect simulations are discussed. Particular calculations for metals, ionic crystals and oxides, are considered. (UK).
Several possibilities of the use of molecular models in quantum-chemical investigations of the structure of defect centers on the surfaces of oxides on nontransition elements have been illustrated. There has been a special discussion of the assumption of the local nature of the chemical interactions in these systems, which underlies such an approach, and of the consequent laws governing the formation of their lattices in the example cases of zeolites, kaolinites, and comparable boron- and aluminum-containing oxides. A quantum-chemical interpretation of the body of experimental data from investigations of the dehydroxylation of H forms of zeolites has been given. The structure of the Lewis acid centers formed as a result, and their chemisorption properties, have been discussed.
The oxidation of n-butylbenzene was studied in a jet-stirred reactor (JSR) at 10atm in dilute conditions providing new experimental results over the low- and high-temperature range 550-1180K, and variable equivalence ratio (0.25ϕ1.5). They consisted of concentration profiles of the reactants, stable intermediates and final products, measured as a function of temperature, at a constant residence time of 1s, by sonic probe sampling followed by on-line GC-MS and off-line GC-TCD-FID and GC-MS analyses. The oxidation of n-butylbenzene in these conditions was modeled using a detailed chemical kinetic reaction mechanism (404 species and 2210 reactions, most of them reversible) deriving from a previous scheme proposed for the ignition, oxidation, and combustion of simple aromatics (benzene,...
A numerical model was developed to simulate the combined effects of heat transfer, magnetite oxidation, and NO{sub x} formation in a grate-kiln furnace for taconite pellet induration. Heat transfer from the flame in the kiln was described by the net radiation method. The shrinking core model was used to account for magnetite oxidation on the grate. A novel approach to oxidation of tumbling pellets in a kiln was derived. The Zeldovich mechanism was used to predict thermal NO generation. Temperature fluctuations in the gas streams were estimated with a clipped Gaussian probability density function. The thermal energy balances and mass balances resulted in coupled systems of first-order differential equations, which were solved numerically. The model is capable of predicting NO production and magnetite oxidation in agreement with observation of ...
Despite the rapid development of literature pertaining to fundamental (1-4) studies of oxidation catalysis, a general theory of heterogeneous selective oxidation catalysis explaining the selectivity behavior of different metal oxide systems has not yet been developed. Redox mechanisms have been widely invoked in the kinetic and mechanistic descriptions of selective oxidation reactions, suggesting a dynamic behavior of hydrocarbon and oxygen interactions with the catalyst surface. Nevertheless, most of the recent theoretical approaches of this subject matter (5-7) are essentially static in nature. Correlations are made with surface structure on the basis of crystallographic considerations with selectivity being related to the nature, number, bond-strength and nearness of oxygen atoms in the neighborhood of adsorption centers. The effect of the reaction medium on the configuration of the catalyst surface, ...
In the present study, models of key chemical processes governing the compositions of the tapped metal from the cupola on the basis of physico-chemical fundamentals have been developed. As evident from the literature survey, the investigations conducted in the past have focused their attention on one phenomenon at a time; for example, a particular chemical reaction, measurement of gas composition or the temperature distribution inside a cupola. Notwithstanding the importance of these studies and their contribution toward the understanding of cupola operation, mathematical models of key chemical processes and their interdependence must be investigated to obtain a complete insight into the various interlinked phenomena occurring inside a cupola. For example, the oxidation of the metallic charge leads to the formation of iron oxide which influences the final content of elements such as silicon, manganese ...
The aim of present study was to evaluate antioxidant property of Glycyrrhiza glabra root extracts using in vitro models. The dose-dependent aqueous and ethanolic extracts demonstrated the scavenging activity against nitric oxide (concentration that caused 50% inhibition of nitric oxide radicals [IC(50)]=72 and 62.1 microg/ml, respectively), superoxide (IC(50)=64.2 and 38.4 microg/ml, respectively), hydroxyl (IC(50)=81.9 and 63 microg/ml, respectively), DPPH (IC(50)=43.6 and 28.3 microg/ml, respectively) and ABTS(*+) (IC(50)=77.3 and 57.2 microg/ml, respectively) radicals. Further, both extracts showed strong reducing power and iron-chelating capacities. In the Fe(2+)/ascorbate system, both extracts were found to inhibit mitochondrial fraction lipid peroxidation. In copper-catalyzed human serum and low-density lipoprotein oxidationmodels, both extracts significantly (P<0.05) ...
Simulations with a regional chemical transport model show that anthropogenic emissions of volatile organic compounds and nitrogen oxides (NOx = NO + NO2) lead to a dramatic diurnal...Full Text Available
Nitric oxide (NO)-based therapies effectively inhibit neointimal hyperplasia in animal models of arterial injury and bypass grafting, but are not available clinically. We created a simple, effective,...Full Text Available
PurposeCataract is the leading cause of blindness and is associated with oxidative damage and protein modification in the lens. In the present study, we have employed proteomic and...Full Text Available
A thermodynamic analysis of the behaviour of Alloy 800 in helium based atmospheres relevant to the High Temperature Gas Cooled Reactor indicates that, depending upon the precise gas composition, oxidation and carburisation, or carburisation alone may be expected. The prime influence appears to be the moisture level. The morphology and structure of the reaction products are discussed. It is shown that the 'reactive' elements chromium, manganese, titanium and silicon are concentrated in the oxide scale which is normally duplex in structure. Aluminium oxide is formed at grain boundaries and in an internal oxidation zone together with titanium and sometimes silicon. In carburising conditions, mixed titanium-chromium carbides are formed. When this occurs, intergranular penetration is maximised. Weight gain data are assessed and briefly described and a tentative model for the mechanism of ...
The structure of hydroxylated oxide films (passive films) formed on Cr(110) in 0.5 M H{sub 2}SO{sub 4} at +0.35, +0.55, and +0.75 V/SHE has been investigated by in situ scanning tunneling microscopy (STM). Cathodic reduction pretreatments at {minus}0.54, {minus}0.64, and {minus}0.74 V/SHE destroy the well-defined topography of the single-crystal electrode and they have been excluded from the passivation procedure. Two different passive film structures have been observed, depending on the potential and time of passivation. At low potential (+0.35 V/SHE), the passive film, consisting mostly of chromium hydroxide, has a noncrystalline and granular structure whose roughness suggests local variations of thickness of ca. {+-} 0.5 nm. A similar structure is observed at higher potential (+0.55 V/SHE), but only for a short polarization time. For longer polarization at 0.55 V/SHE, and at higher potentials (+0.75 V/SHE), a crystalline structure is formed; the higher the ...
AGNES is a chopper spectrometer installed at the top of the C3 cold guide of JRR-3 (JAERI, Tokai). In 2004 - 2006, this spectrometer was greatly improved by installing (1) 208 new detectors to make the detector bank complete, (2) new radiation shields composed of Fe (14 mm), polyethylene (50 mm), B4C rubber (10 mm), and Cd (0.5 mm) sheets, (3) a new control system for the anti-frame-overlap chopper rotating simultaneously with the Fermi chopper, (4) a monitor counter at the space between the chopper and monochromator, (5) a neutron guide tube (50 cm) before the monochromator, (6) a new instrument control (monochromators, choppers, beam narrowers, etc.) and measurement control (real-time data monitoring, sample temperature control, etc.) systems, (7) a top-loading type cryostat workable at a wide temperature range of 6 - 480 K. As the results of these improvements, the signal intensity has been increased by 3.3 and the ...
The electrical transport taking place in the {mu}c-Si tunnel recombination junction (TRJ) of a-Si:H/a-Si:H tandem solar cells and the role of CO{sub 2} plasma oxidation performed between microcrystalline layers is investigated in this paper with the computer code AMPS. Oxidized interfaces were modelled as simple highly defective intrinsic {mu}c-Si layers. Two different tunnel junction structures are studied in this paper: (a) (n){mu}c-Si/oxide/(p){mu}c-Si and (b) (n){mu}c-Si/(i){mu}c-Si/(p){mu}c-Si. In the last configuration the oxide interface is removed and replaced by a thin defective (i) {mu}c-Si layer. Both tunnel junctions have comparable theoretical and experimental tandem solar cell efficiencies which indirectly proves that our modelling assumption for oxidised interfaces is correct. A-Si:H/a-Si:H tandem solar cell efficiencies depend on the thickness of ...
This report summarizes the work performed by Honeywell during the October 2001 to December 2001 reporting period under Cooperative Agreement DE-FC26-01NT40779 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid Oxide Fuel Cell Hybrid System for Distributed Power Generation''. The main objective of this project is to develop and demonstrate the feasibility of a highly efficient hybrid system integrating a planar Solid Oxide Fuel Cell (SOFC) and a turbogenerator. The conceptual and demonstration system designs were proposed and analyzed, and these systems have been modeled in Aspen Plus. Work has also started on the assembly of dynamic component models and the development of the top-level controls requirements for the system. SOFC stacks have been fabricated and performance mapping initiated.
The rate was studied of radiation destruction of phenol aqueous solutions at a concentration range of 1 to 100 ppm. Irradiated were model solutions containing additions of some organic and inorganic substances typical of the petrochemical industry. In view of the fact that the radiation destruction kinetics is determined by the amount of dissolved oxygen in the sample and by the phenol concentration, relatively low doses were used. Thus, a sufficient amount of oxygen in the sample and therefore the oxidation mechanism of radiolysis were ensured. The dose-response relationships for phenol destruction were studied using doses of 50, 100, 200 and 400 J.kg"-"1; the limit dose was 500 J.kg"-"1. From the results obtained, a kinetic model was constructed of radiation phenol oxidation in aqueous solutions in the presence of various organic and inorganic additions. (B.S.).
The present volume on modeling of batteries and fuel cells discusses the significance of the effectiveness factor for flooded porous electrodes, active pore distribution spectroscopy for characterizing porous battery electrodes, the agglomerate model for porous electrodes, and dynamic-performance measurements of battery cells for electric vehicles and other applications. Attention is given to mathematical modeling of a primary zinc/air battery, mathematical modeling of Grace Li-TiS2 cells, modeling of electrocrystallization processes in battery systems, and rotating disk electrode studies in molten Li/K carbonate eutectic. Topics addressed include the variability of nickel oxide cathode dissolution in molten carbonate fuel cells, water transport properties of fuel cell ionomers, modeling water content effects in polymer electrolyte fuel ...
Lean premixed combustion (LPC) of natural gas is of considerable interest in land-based gas turbines for power generation. However, modeling such combustors and adequately addressing the concerns of LPC, which include emissions of nitrogen oxides, carbon monoxide and unburned hydrocarbons, remains a significant challenge. In this paper, characteristics of published simulations of gas turbine combustion are summarised and methods of modeling turbulent combustion are reviewed. The velocity-composition PDF method is selected for implementation in a new comprehensive model that uses an unstructured-grid flow solver. Reduced mechanisms for methane combustion are evaluated in a partially stirred reactor model. Comprehensive model predictions of swirl-stabilised LPC of natural gas are compared with detailed measurements obtained in a laboratory-scale combustor. The ...
A three-dimensional computational fluid dynamics (CFD) electrochemical model has been created to model high-temperature electrolysis stack performance and steam electrolysis in the Idaho National Laboratory (INL) Integrated Lab Scale (ILS) experiment. The model is made of 60 planar cells stacked on top of each other operated as Solid Oxide Electrolysis Cells (SOEC). Details of the model geometry are specific to a stack that was fabricated by Ceramatec, Inc. and tested at INL. Inlet and outlet plenum flow and distribution are considered. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user ...
The emission of air pollutants from road vehicles is the most significant source of air pollution in towns. The chemical composition of these pollutive substances is dependent on the fuel, the type of vehicle and the character of the traffic system. The pollution concentration was measured, (nitrogen oxides and carbon monoxide) in relation to each type of vehicle, in four streets in the Copenhagen area. The system of measurement used was the ''Operational Street Pollution Model'' (OSPM). Results are presented in the form of tables and charts. (AB) 11 refs.
The Advanced Statistical Trajectory Regional Air Pollution (ASTRAP) model simulates long-term transport and deposition of oxides of and nitrogen. t is a potential screening tool for assessing long-term effects on regional visibility from sulfur emission sources. owever, a rigorou...
A simple model is described to simulate kinetic processes in dielectric barrier discharges for O_2/NO_x mixtures. A threshold of ozone production found experimentally is confirmed by the calculations of this modeling, and the underlying chemical reaction mechanisms are discussed. It is also found that the effects of diffusion processes in the period of the lifetime of O atoms are not important to micro-discharge channels with a large radius, i.e. larger than 150 #mu#m
A model has been developed to predict the chemical composition of lakes that form in pyrite-bearing open-pit mines. Pyrite oxidation in wall rock releases sulfuric acid and metals, which mix with ground waters in the lake. Aqueous metal concentrations are calculated using MINTEQA2.
A method of kinetic analysis applicable to non-isothermal oxidation processes of ceramic nanocomposites is presented using Ti-Si-C-N powder as the substrate. The nanoparticle size and phase composition were determined using high-resolution transmission electron microscopy and X-ray diffraction (XRD). Thermogravimetric measurements were carried out for powder samples in dry air in the temperature range 298-1770 K. The following heating rates were applied: 3, 5, 10, 20 K min{sup -1}. Mass spectrometry was used to analyze gaseous oxidation products and solid products were identified by the XRD technique. The Coats-Redfern equation was applied for the kinetic analysis. For each stage of the oxidation kinetic models, the best accuracy was achieved using a series of criteria, and then the A and E parameters of the Arrhenius equations were estimated. Both linear regression and artificial neural networks were ...
Astrocyte dysfunction is implicated in course of various age-related neurodegenerative diseases. Chronic injection of D-galactose can cause a progressive deterioration in learning and memory capacity and serve as an animal model of aging. To investigate the involvement of astrocytes in this model, oxidative stress biomarkers, biochemical and pathological changes of astrocytes were examined in the hippocampus of the rats with six weeks of D-galactose injection. D-galactose-injected rats displayed impaired antioxidant systems, an increase in nitric oxide levels, and a decrease in reduced glutathione levels. Consistently, western blotting and immunostaining of glial fibrillary acidic protein showed extensive activation of astrocytes. Double-immunofluorescent staining further showed activated astrocytes highly expressed inducible nitric oxide synthase. Electron microscopy demonstrated ...
A detailed study was undertaken to examine the potential of iron oxide present in red mud (a waste product from Bayer's alumina process) as a sorbent for SO/sub 2/ capture by dry process. The other constituents present in the red mud can bring about enhanced utilization of the active component provided they are almost completely inert. The practical use of the process has been explored and a few batchwise cyclic operations of SO/sub 2/ capture and regeneration have also been carried out. A kinetic model of the reaction has been proposed.
Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation ...
Photocurrent and capacitance measurements of semiconductor passive films formed on metals and alloys can be used to study the electronic properties and reveal indirect information about structure and composition. The current work used these techniques to investigate the electronic properties of the passive films formed on three austenitic stainless steels, types 304L, 316L and 254SMO, in borate. Evidence was found for the existence of a large number of localised mid bandgap states, consistent with amorphous oxides. However, the flat-band potentials of the austenitic stainless steel passive films were found to be independent of both composition and measuring frequency. The most credible explanation for the bandgap values determined from photocurrent measurements is that the passive films are formed as dual layers, iron oxide outer layer and chromium oxide inner layer. This model does not need to evoke ...
Photocurrent and capacitance measurements of semiconductor passive films formed on metals and alloys can be used to study the electronic properties and reveal indirect information about structure and composition. The current work used these techniques to investigate the electronic properties of the passive films formed on three austenitic stainless steels, types 304L, 316L and 254SMO, in borate. Evidence was found for the existence of a large number of localised mid bandgap states, consistent with amorphous oxides. However, the flat-band potentials of the austenitic stainless steel passive films were found to be independent of both composition and measuring frequency. The most credible explanation for the bandgap values determined from photocurrent measurements is that the passive films are formed as dual layers, iron oxide outer layer and chromium oxide inner layer. This model does not need to evoke ...
The oxidation of carbon black, CB, in presence of CeO{sub 2} is investigated to gain a better understanding of the effect of the contact between the two solids during this reaction. Different CB/CeO{sub 2} mixtures are tested in a fixed bed reactor. The experimental data are used to propose a model for CB oxidation in presence of CeO{sub 2}. It accounts for the size distribution of CeO{sub 2} particles, the contact area between CB and CeO{sub 2}, the mass of CB in the sample and the initial ratio CB/CeO{sub 2}. Corresponding kinetic parameters are determined. 35 refs., 10 figs., 3 tabs.
Passive films formed on Alloy 690 in high-temperature alkaline environments were investigated by potentiodynamic polarization, X-ray photoelectron spectroscopy, transmission electron microscopy and Mott-Schottky approach. Passive current density and donor density of the passive films increase with increasing temperature, due to increased diffusion rates of metallic ions and dehydration of hydroxide phases. The passive films show a duplex structure including an inner layer of fine-grained Cr oxide or spinel oxide and an outer layer of Ni-Fe spinel oxide and Ni hydroxide. A growth model of the passive films on Alloy 690 in high-temperature alkaline environments is proposed and discussed.
Passive films formed on Alloy 690 in high-temperature alkaline environments were investigated by potentiodynamic polarization, X-ray photoelectron spectroscopy, transmission electron microscopy and Mott-Schottky approach. Passive current density and donor density of the passive films increase with increasing temperature, due to increased diffusion rates of metallic ions and dehydration of hydroxide phases. The passive films show a duplex structure including an inner layer of fine-grained Cr oxide or spinel oxide and an outer layer of Ni-Fe spinel oxide and Ni hydroxide. A growth model of the passive films on Alloy 690 in high-temperature alkaline environments is proposed and discussed.
The primary coolant oxidises the surfaces of construction materials in nuclear power plants. The properties of the oxide films influence significantly the extent of incorporation of actuated corrosion products into the primary circuit surfaces, which may cause additional occupational doses for the maintenance personnel. The physical and chemical properties of the oxide films play also an important role in different forms of corrosion observed in power plants. This report gives a short overview of the factors influencing activity build-up and corrosion phenomena in nuclear power plants. Furthermore, the most recent modifications in the water chemistry to decrease these risks are discussed. A special focus is put on zinc water chemistry, and a preliminary discussion on the mechanism via which zinc influences activity build-up is presented. Even though the exact mechanisms by which zinc acts are not yet known, it is assumed that Zn may block the ...
Cementitious materials provide an ideal geochemical environment (e.g., high pH pore fluids and large surface areas for sorption) for immobilizing nuclear waste. The inclusion of reducing agents, such as blast furnace slag (BFS) can immobilize radionuclides by forming of solid sulfide phases. Thermodynamic calculations using the MINTEQ geochemical computer code indicate the elemental sulfur present in BPS reacts with the highly mobile pertechnetate anion (TcO{sub 4}{sup -}) anion to form an insoluble technetium sulfide phase (Tc{sub 2}S{sub 7(s)}). Initially, the waste form very effectively immobilizes technetium. However, as oxygen diffuses into the waste form, an outer zone of oxidized concrete and a shrinking core of reduced intact concrete develops. Oxidation of sulfur in the outer zone results in increased technetium concentrations in the pore fluid because Tc{sub 2}S{sub 7(a)} oxidizes to the mobile TcO{sub 4}{sup -} ...
Hyperphosphorylated and aggregated human protein tau constitutes a hallmark of a multitude of neurodegenerative diseases called tauopathies, exemplified by Alzheimer's disease. In spite of an enormous amount of research performed on tau biology, several crucial questions concerning the mechanisms of tau toxicity remain unanswered. In this paper we will highlight some of the processes involved in tau biology and pathology, focusing on tau phosphorylation and the interplay with oxidative stress. In addition, we will introduce the development of a human tau-expressing yeast model, and discuss some crucial results obtained in this model, highlighting its potential in the elucidation of cellular processes leading to tau toxicity.
A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with ...
The percolated or active triple phase boundary (TPB) length per unit volume of Ni-YSZ anode hollow fibers (HFs) containing 60wt.% initial NiO and a spatially varying microstructure were measured using a focused ion beam (FIB)-SEM technique. The measured values of contiguous TPB density were interfaced with a 2-D distributed finite element model of a hollow fiber solid oxide fuel cell. The model was applied to simultaneously solve the ionic and electronic charge balances in the electrodes, which were modelled as overlying continuum materials with effective electronic and ionic conductivities. The model was used to predict the effects of anode microstructure on the distribution of current density, and anode activation polarization. Active TPB lengths of 2.63-8.63 m^-^2 were measured for the ...
An electrochemistry model was developed to analyse the J-V characteristics of a Proton Exchange Membrane (PEM) water electrolyzer for hydrogen production. The Butler-Volmer equation and water transport characteristics through electrolyte membrane were employed to simulate the electrode activation over-potential and membrane ohmic over-potential, respectively. The modeling results are found to agree reasonably well with experimental data published in the literature. The parametric simulations show that the ohmic over-potential is relatively small with typical water content in the membrane. Compared with the cathode over-potential, the anode over-potential is more significant and constitutes the major source of voltage loss. The high anode over-potential is due to the relatively slow oxidation kinetics, which is related to anode material property and microstructure. This model can be integrated with a ...
Papers are presented on the modeling, dispersion, formation, transformation, monitoring and biological effects of atmospheric pollution. Specific topics include a prognostic mesoscale model for pollutant transport and diffusion, commuter exposure modeling, a Gaussian plume model for an urban area, carbon monoxide dispersion in an urbanized area, wind-tunnel modeling of flue gas dispersion, the regional-scale transport of fine aerosol components in eastern North America, and a Markov process for the generation of hourly average wind vectors. Attention is also given to photochemical aerosol formation in multicomponent systems, heterogeneous nitrogen oxide-particulate reactions, the generation and measurement of primary soot aerosols of size between 50 and 400 A, inertial particle size classification techniques, the design of air quality monitoring networks, ...
An experimental and modelling study was performed for a reverse flow catalytic converter attached to a natural gas/diesel dual fuel engine. The catalytic converter had a segmented ceramic monolith honeycomb substrate and a catalytic washcoat containing a predominantly palladium catalyst. A one-dimensional single channel model was used to simulate the operation of the converter. The kinetics of the CO and methane oxidation followed first-order behaviour. The activation energy for the oxidation of methane showed a change with temperature, dropping from a value of 129 to 35 kJ/mol at a temperature of 874 K. The reverse flow converter was able to achieve high reactor temperature under conditions of low inlet gas temperature, provided that the initial reactor temperature was sufficiently high. (author)
Net heats of reaction were measured in an isothermal calorimeter for both single phase (organic) and two phase (organic and aqueous) TBP/HNO{sub 3} reacting solutions at temperatures above 100 C. The oxidation rate constant was determined to be 5.4E-4 min{sup {minus}1} at 110 C for an open ``vented`` system as compared to 1.33 E-3 min{sup {minus}1} in the closed system. The heat released per unit material oxidized was also reduced. The oxidation in both phases was found to be first order in nitric acid and pseudo-zero order in butylnitrate and water. The hydrolysis (esterification) rate constant determined by Nichols` (1.33E-3 min{sup {minus}1}) fit the experimental data from this work well. Forced evaporation of the volatile components by the product gases from oxidation resulted in a cooling mechanism which more than balanced the heat from the oxidation reaction in the two-phased ...
The aim of this work is to account for the effects of the high temperature oxidation of metals on their microstructure and their mechanical properties. 'Model' materials like pure nickel, pure iron and the Ni-20Cr alloy are studied. Nickel foils have been oxidised at 1000 C on one side only in laboratory air, the other side being protected from oxidation by a reducing atmosphere. After the oxidation treatment, the unoxidized face was carefully examined by using an Atomic Force Microscope (AFM). Grain boundaries grooves were characterised and their depth were compared to the ones obtained on the same sample heat treated in the reducing atmosphere during the same time. They are found to be much deeper in the case of the single side oxidised samples. It is shown that this additional grooving is directly linked to the growth of the oxide scale on the opposite side and ...
The influence of high energy electron (23 MeV) irradiation on the electrical characteristics of p-channel polysilicon thin film transistors (PSTFTs) was studied. The channel 220 nm thick LPCVD (low pressure chemical vapor deposition) deposited polysilicon layer was phosphorus doped by ion implantation. A 45 nm thick, thermally grown, SiO{sub 2} layer served as gate dielectric. A self-alignment technology for boron doping of the source and drain regions was used. 200 nm thick polysilicon film was deposited as a gate electrode. The obtained p-channel PSTFTs were irradiated with different high energy electron doses. Leakage currents through the gate oxide and transfer characteristics of the transistors were measured. A software model describing the field enhancement and the non-uniform current distribution at textured polysilicon/oxide interface was developed. In order to assess the irradiation-stimulated changes of gate ...
The influence of high energy electron (23 MeV) irradiation on the electrical characteristics of p-channel polysilicon thin film transistors (PSTFTs) was studied. The channel 220 nm thick LPCVD (low pressure chemical vapor deposition) deposited polysilicon layer was phosphorus doped by ion implantation. A 45 nm thick, thermally grown, SiO_2 layer served as gate dielectric. A self-alignment technology for boron doping of the source and drain regions was used. 200 nm thick polysilicon film was deposited as a gate electrode. The obtained p-channel PSTFTs were irradiated with different high energy electron doses. Leakage currents through the gate oxide and transfer characteristics of the transistors were measured. A software model describing the field enhancement and the non-uniform current distribution at textured polysilicon/oxide interface was developed. In order to assess the irradiation-stimulated changes of gate ...
The main drawback of Ni/YSZ anode supports for solid oxide fuel cell application is their low tolerance to reducing and oxidizing (RedOx) atmosphere changes, owing to the Ni/NiO volume variation. This work describes a structured approach based on design of experiments for optimizing the microstructure for RedOx stability enhancement. A full factorial hypercube design and the response surface methodology are applied with the variables and their variation range defined as: (1) NiO proportion (40-60wt% of the ceramic powders), (2) pore-former proportion (0-30wt% corresponding to 0-64vol.%), (3) NiO particle size (0.5-8mm) and (4) 8YSZ particle size (0.6-9mm). To obtain quadratic response models, 25 different compositions were prepared forming a central composite design. The measured responses...
The aim of this study was to evaluate the potential of low-resolution Raman spectroscopy for monitoring the oxidation status of olive oil. Primary and secondary oxidation parameters such as peroxide value, K"2"3"2 and K"2"7"0 were studied. Low-resolution Raman spectra ranging from 200 to 2700 cm^-^1 in a set of 126 oxidized and virgin olive oil samples were collected directly using a probe. Partial Least Squares was used to calibrate the Raman instrument for the different targeted parameters. The performance of the models was determined by using validation sets, and the best results obtained were: R^2 = 0.91, RMSEP = 2.57 for the peroxide value content; R^2 = 0.88, RMSEP = 0.37 for K"2"3"2; and R^2 = 0.90, RMSEP = 0.08 for K"2"7"0. These results demonstrated that low-resolution Raman spect...
This report documents the development and use of the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. The model, developed in a spreadsheet format, estimates the full fuel- cycle emissions and energy use associated with various transportation fuels for light-duty vehicles. The model calculates fuel-cycle emissions of five criteria pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, sulfur oxides, and particulate matter measuring 10 microns or less) and three greenhouse gases (carbon dioxide, methane, and nitrous oxide). The model also calculates the total fuel-cycle energy consumption, fossil fuel consumption, and petroleum consumption using various transportation fuels. The GREET model includes 17 fuel cycles: petroleum to conventional gasoline, reformulated ...
Careful sample preparation and secondary ion mass spectroscopy have been used to characterize arsenic dose loss to the silicon-oxide interface. Using high resolution x-ray photoelectron spectroscopy for microprofiling, we have directly observed the pileup of arsenic at the silicon dioxide-silicon interface. At least half of the pileup is shown to be on the silicon side of the interface in the first monolayer of silicon. Monolayer chemical oxidation and etching are successfully used to profile this pileup in silicon. This pileup contains most of the arsenic dose loss that occurs during transient enhanced diffusion. This result is crucial to correctly model the dose loss and provides physical justification for using a trap/detrap model at the interface, which is necessary to account for the fact that the arsenic surface concentration remains constant during an anneal and the fact that the dose loss is ...
Careful sample preparation and secondary ion mass spectroscopy have been used to characterize arsenic dose loss to the silicon-oxide interface. Using high resolution x-ray photoelectron spectroscopy for microprofiling, we have directly observed the pileup of arsenic at the silicon dioxide-silicon interface. At least half of the pileup is shown to be on the silicon side of the interface in the first monolayer of silicon. Monolayer chemical oxidation and etching are successfully used to profile this pileup in silicon. This pileup contains most of the arsenic dose loss that occurs during transient enhanced diffusion. This result is crucial to correctly model the dose loss and provides physical justification for using a trap/detrap model at the interface, which is necessary to account for the fact that the arsenic surface concentration remains constant during an anneal and the fact that the dose loss is ...
It is demonstrated that normal pitting can occur during oxidizing conditions in the repository. It is also concluded that a new theory for pitting corrosion has to be developed, as the present theory is not in accordance with all practical and experimental observations. A special variant of pitting, based on the growth of sulfide whiskers, is suggested to occur during reducing conditions. However, such a mechanism needs to be demonstrated experimentally. A simple calculational model of canister corrosion was developed based on the results of this study. 69 refs, 3 figs.
Analysis of the coke gas combustion porcess is presented. Standard kinetic relationships were utilized. Calculations were performed for coke gas with high and low content of H/sub 2/ and for blasting air 20 and 100/sup 0/C. Temperature relationships, composition of gas combustion products and release of nitrogen oxides were determined. Results are analyzed which will make it possible to control the composition of combustion products.
The influence of RTA (Rapid Thermal Anneal) treatment on MOS radiation hardness is demonstrated and compared with classical furnace treatment. In the case of the RTA, the oxide trapped charge is found to depend on: (i) the anneal temperature as expected, data are in good agreement with a recently developed model of oxygen out-diffusion; (ii) the location across the wafer with a radial dependence, results could be related to stress induced by thermal gradient.
One of several methods to build YSZ electrolyte of SOFC is plasma spraying. This system heats particle to a melting point and then pushing them into target and forming a deposition. This paper presents heating studies of YSZ particle in plasma jet. By simple model it is shown that the required time such those YSZ particle with grain size of 50 ?m to be melt is around 12 x 10-4 second. (author)
The effect of the degree of degradation of the components of a model municipal plastic waste (a mixture of low-density polyethylene, high-density polyethylene, polypropylene and high-impact polystyrene) on the toughness and stability of recyclates compatibilised with a cooperative compatibilisation system (a mixture of ethylene-propylene statistical and styrene-butadiene block copolymers with a secondary amine-based stabiliser) was studied. It was shown that good impact strength was achieved for recyclates having components with a low or medium degree of degradation. Mechanical properties of recyclates having the components with a high degree of degradation are deteriorated. The addition of the cooperative compatibilisation system leads to a higher thermo-oxidative stability of recyclates ...
Smooth and notched specimens of the bearing steel 100Cr6 (SAE 52100) in a bainitic condition were used to determine the S-N-curves under tensile, torsional and combined in- and out-of-phase loading. In the area of high-cycle-fatigue, crack initiation was most likely caused by inclusions like Titanium Carbonitrides or Aluminium Oxides. A model was developed to describe the influence of the magnitude of these inclusions on the lifetime. A weakest link model, using the statistical distribution of inclusions and surface flaws, was used to describe the fatigue limit. (orig.)
We propose a dissolution-passivation model to account for the electrochemical behavior of Alloy 800 and 316L stainless steel under steam generators operating conditions. This model is similar to the one defined for nickel, considering the known importance of this element on the studied alloys. The comparison of the rates of the elementary steps points out the favorable influence of dissolved oxygen and phosphate ions on the dissolution of Alloy 800, even in the presence of chloride ions. The sensitivity of 316L SS is greater, especially because of the lowest stability of oxide-like intermediate.
We propose a dissolution-passivation model to account for the electrochemical behavior of Alloy 800 and 316L stainless steel under steam generators operating conditions. This model is similar to the one defined for nickel, considering the known importance of this element on the studied alloys. The comparison of the rates of the elementary steps points out the favorable influence of dissolved oxygen and phosphate ions on the dissolution of Alloy 800, even in the presence of chloride ions. The sensitivity of 316L SS is greater, especially because of the lowest stability of oxide-like intermediate.
A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.
Formaldehyde oxidation was examined in a laboratory reactor over alumina-supported Pt, Pd, Rh, Ag, Cu-Cr, and Pd-Ag catalysts as part of a program to develop catalysts for lean-exhaust methanol-fueled vehicles. In general, the H/sub 2/CO oxidation behavior of the catalysts paralleled the CH/sub 3/OH oxidation behavior reported in Parts 1 and 2 of this series (Appl. Catal. 27(1986) 83; J. Catal. 103(1987) 419). Principal similarities were: high activity of Pt when there was no carbon monoxide (CO) in the feed, but strong inhibition by added CO; lower activity of Ag and Cu-Cr catalysts, but only weak inhibition due to added CO; enhanced activity of the Pd-Ag catalyst compared to Pd and Ag alone for feeds containing CO in addition to H/sub 2/CO; and, relatively poor activity of the Rh catalyst. The most unusual behavior was observed with the Pd catalyst, which showed local minima in the H/sub 2/CO conversion vs. temperature ...
The vast majority of fundamental studies of metal oxide selective oxidation catalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxide catalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox catalyst is still lacking. In an effort to provide an understanding and a physical basis for ...
To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the ...
In this thesis the rate constants for a number of radical reactions in aqueous solution have been studied in a wide temperature range. The reactions of H with H_2O_2, OH and HO_2 and the reactions of HO_2 with OH, Fe"2"+ and Cu"2"+ have been studied. For each reaction rate constants have been determined as a function of temperature using the technique of high temperature, high pressure (HTP) pulse radiolysis. The rate constants were obtained by fitting a kinetic computer model to the experimental data. From an Arrhenius plot the activation energy of each reaction was determined. The data determined in this way are important for modeling of radiolysis in nuclear light water reactors. A previously developed model for calculation of the effect of water radiolysis products on oxidation and dissolution of spent nuclear fuel has been improved. In the new model, called TraRaMo, ...
A mathematical model of a mineral melting cupola furnace for stone wool production has been developed for improving cupola operation. The 1-D, first-engineering-principles model includes mass and heat balances for the gas phase, five solid phases, and four liquid phases. The gas and solid/liquid phases flow countercurrently. Seven chemical reactions account for the conversions of coke, iron oxide, limestone, and gaseous species. The heterogeneous reactions of coke conversion are limited by both kinetics and mass transport. Heat transfer between phases is modeled including both convection and radiation. The model predicts gas concentrations; mass flow rates; and temperature profiles of the solid, melt, and gas in the cupola, as well as heat loss to the water-cooled walls. Inputs to the model include the coke, rock, and blast air properties, the blast air amount, ...
Grout has been evaluated as a means of containing low-level radioactive waste for long-term disposal. Concerns about hydrogen and reactive gas generation in the Hanford Site grout disposal facility lead to the development of the G3 model, which has predicted buildup of radiolytically formed gases in the grout region and their migration to air-filled regions. The G3 model is a one-dimensional code that couples models of gas diffusion with two-phase gas and liquid flow. It was coupled to a compartment diffusion model and these models predicted the concentrations of hydrogen I nitrous oxide, and other gases in air-filled regions of the grout disposal facility. The results have served as the technical basis for safety studies. A unique finding of the G3 model was that a liquid return, or expulsion of unbound liquid from the grout region, could ...
In pre-experiments a tubular reactor was checked whether it is suitable for kinetic measurement on the system of the silver-catalysed partial oxidation of methanol to formaldehyde. Detrimental effects of heat-transfer and mass-transfer on the experimental results were ruled out. Investigations on the characteristics of the reaction showed that it is possible to manipulate the composition of the product mixture by changing the inlet concentration of the reactants. A modified power-law model was established to describe the reaction kinetics. It considers the preadsorption step of oxygen on the catalysts surface and fits the experimental data quite well. During the rapid oxidation the catalysts surface undergoes a drastic change. It gets coarse and has an adsorption capacity of 11 m{sup 2}/g after being exposed to the reaction mixture. (orig.)
Pre-amorphization of ultrashallow implanted boron in Silicon-on-insulator is optimized to produce an abrupt box-like doping profile with negligible electrical deactivation and significantly reduced transient enhanced diffusion. The effect is achieved by positioning the as-implanted amorphous/crystalline interface close to the buried oxide interface, to minimize interstitials whilst leaving a single-crystal seed to support solid-phase epitaxy. Based on a simple physical model of our results, we estimate that the interface between the Si overlayer and the buried oxide is an efficient interstitial sink with a recombination length of the order of 10nm or less under our experimental conditions. (author)
A three-dimensional mathematical thermo-fluid model coupling the electrochemical kinetics with fluid dynamics was developed to simulate the heat and mass transfer in planar anode-supported solid oxide fuel cell (SOFC). The internal reforming reactions and electrochemical reactions of carbon monoxide and hydrogen in the porous anode layer were analyzed. The temperature, species mole fraction, current density, overpotential loss and other performance parameters of the single cell unit were obtained by a commercial CFD code (Fluent) and external sub-routine. Results show that the current density produced by electrochemical reactions of carbon monoxide cannot be ignored, the cathode overpotential loss is the biggest one among the three overpotential losses, and that the proper decrease of the operating voltage leads to the increase of the current density, PEN structure temperature, fuel utilization factor, fuel efficiency and power output of the ...
This paper reports the results of leaching experiments conducted with and without Thiobacillus ferroxidans at the same conditions in solution. The extent of leaching of ZnS with Bacteria is significantly higher than that without bacteria at high concentrations of ferrous ions. A porous layer of elemental sulfur is present on the surfaces of the chemically leached particles, which no sulfur is present on the surfaces of the bacterially leached particles. The analysis of the data using the shrinking-core model shows that the chemical leaching of ZnS is limited by the diffusion of ferrous ions through the sulfur product layer at high concentrations of ferrous ions. The analysis of the data shows that diffusion through the product layer does not limit the rate of dissolution when bacteria are present. This suggests that the action of T.ferroxidans in oxidizing the sulfur formed on the particle surface is to remove the barrier to diffusion by ...
Using carbon-paste-CuFeS{sub 2} electrodes and a cyclic voltammetric technique, it was found that a large number of intermediate electrochemical oxidation reactions were associated with the dissolution of chalcopyrite in presence and absence of bacteria. The effects of concentrations of copper, ferrous and ferric ions, as well as of agitation on the peaks of cyclic voltammograms were measured. It was established that chalcopyrite oxidation was solid-state controlled as suggested by the data of chronopotentiometric and chronoamperometric measurements. The activation energy of solid state diffusion of chalcopyrite leaching was determined by the Sand's method to be {triangle}E{sub a} = 20.5 kJ. The leaching mechanism is discussed in terms of solid-state properties (energy bonding) of the n-type semiconductor chalcopyrite and energy density states of redox systems of acidic bacterial leach media. A generalized model ...
Pitch-based short carbon fibers (CFs) were treated by air oxidation and cryogenic nitrogen, respectively. Thereafter the treated and untreated CFs were incorporated into polyimide (PI) matrix to form composites. The CFs before and after treatment were examined by XPS and SEM.The flexural strength of the specimen was determined in a three-point test machine and the tribological properties of PI composites sliding against GCr15 steel rings were evaluated on an M-2000 model ring-on-block test rig. The results show that the surface of the treated CFs became rougher. Lots of active groups formed on the CF surface after air oxidation.The treatment can effectively improve the mechanical and tribological properties in their PI composites due to the enhanced fiber-matrix interfacial bonding. Copyri...
The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U{sub 3}O{sub 8} was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U{sub 3}O{sub 8} and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li{sub 2}Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool.
In energy industries, it is always of difficulty to produce high heat value(HHV) gas continuously using pulverized coal. In this paper, a new type furnace for partitioned alternative gasification using pulverized coal is developed, in which the oxidation and reduction reaction occur alternatively with the dropping of pulverized coal and finally HHV gas could be continuously obtained at the reduction zone exit and low heat value(LHV) gas at the oxidation zone exit. Furthermore, the gasification characteristics and their factors in furnace are numerically simulated under two dimensional model with a self-coded program, based on heat, mass and energy transfer as well as reaction principles. It is found that the producing rate of HHV gas is 1.10Nm3/kg with heat value of 11.72MJ/Nm3, however, t...
Chemical characterization of passive films formed on AISI 304 austenitic stainless steel, in a borate/boric acid solution at pH 9.2, under various conditions of potential, temperature, and polarizations time, was made by Auger electron spectroscopy combined with ion sputtering, and x-ray photoelectron spectroscopy (XPS). The depth chemical composition, thickness, and duplex character of the passive layers were determined after processing AES sputter profiles by their quantitative approach based on the sequential layer sputtering model. Moreover, separated contributions of elements in their oxidized and unoxidized state could be disclosed from part to part of the oxide-alloy interface. The XPS study specified the chemical bondings which take placed inside the film, between Fe and oxygen (and water).
The aim of this work is to simulate the reduction by hydrogen of the tri-uranium octo-oxide U{sub 3}O{sub 8} (obtained by uranium trioxide calcination) into uranium dioxide. The kinetics curves have been obtained by thermal gravimetric analysis, the hydrogen and steam pressures being defined. The geometrical modeling which has allowed to explain the trend of the kinetics curves and of the velocity curves is an anisotropic germination-growth modeling. The powder is supposed to be formed of spherical grains with the same radius. The germs of the new UO{sub 2} phase appear at the surface of the U{sub 3}O{sub 8} grains with a specific germination frequency. The growth reactivity is anisotropic and is very large in the tangential direction to the grains surface. Then, the uranium dioxide growths inside the grain and the limiting step is the grain surface. The variations of the growth reactivity and of the germination specific ...
The spectral dependences of absorption photoinduced in a pure bismuth titanium oxide crystal by 532-nm laser pulses are studied. It is shown that optical absorption in the crystal in the range from 492 to 840 nm increases with increasing exposure. The photoinduced absorption relaxes in the dark for more than 60 hours. A model of photoinduced absorption is proposed which assumes the population of two trap centres with the normal energy distribution law for the concentrations of electrons photoexcited from donors to the conduction band. This model well describes the spectral dependences of photoinduced absorption by using the average ionisation energies of the traps E{sub 1} = 1.60 eV and E{sub 2} = 2.57 eV. The model is used to estimate the increase in the photorefractive sensitivity of a bismuth titanium oxide crystal in the near IR region, which was earlier observed after exposing ...
A strategic partnership was formed among the American Foundrymen`s Society and the Federal government to develop and transfer the technology needed by the US foundry industry to: increase energy efficiency of cupola melting; improve recovery of carbon, silicon, and manganese through reduced oxidation losses; and improve productivity due to more uniform and predictable iron compositions. An effective mathematical model of the cupola offers a solution to the complex and interactive chemical and heat transfer processes to melt cast iron. The transient changes in charge size, charge composition, blast rate, and coke rate are used to optimize operation to improve melting rates, minimize oxidation losses of valuable alloying elements (C, Si, and Mn), and maintain iron composition. Despite these challenges, the cupola produces iron at a lower cost, and have better environmental controls than other melting process with 70% of ...
Chemical looping combustion (CLC) is a process in which an oxygen carrier is used for fuel combustion instead of air or pure oxygen as shown in the figure below. The combustion is split into air and fuel reactors where the oxidation of the oxygen carrier and the reduction of the oxidized metal occur respectively. The CLC system provides a sequestration-ready CO2 stream with no additional energy required for separation. This major advantage places combustion looping at the leading edge of a possible shift in strict control of CO2 emissions from power plants. Research in this novel technology has been focused in three distinct areas: techno-economic evaluations, integration of the system into power plant concepts, and experimental development of oxygen carrier metals such as Fe, Ni, Mn, Cu, and Ca. Our recent thorough literature review shows that multiphase fluid dynamics modeling for CLC is not available in the ...
The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth s carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (0.19 PgC yr 1), 3-D spatially-distributed emissions from aviation (0.16 PgC yr 1), and 3-D chemical production of CO2 (1.05 PgC yr 1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a ...
An all solid-state kicker pulser for a proton radiography system has been designed. Multiple solid-state modulators stacked in an inductive-adder configuration are utilized in this kicker pulser design. Each modulator is comprised of multiple metal-oxide-semiconductor field-effect transistors (MOSFETs) which quickly switch the energy storage capacitors across a magnetic induction core. Metglas is used as the core material to minimize loss. Voltage from each modulator is inductively added by a voltage summing stalk. A circuit model of a prototype inductive adder kicker pulser modulator has been developed to predict the performance of the pulser modulator. The modeling results are compared with experimental data.
Selective catalytic reduction (SCR) is a method of reducing the emissions of nitrogen oxides into the atmosphere. Peerless Manufacturing Co. specialises in designing and building SCR systems. The company uses fluid flow modelling to design systems, creating physical and/or numerical flow models to normalise the flow and eliminate potential problems. Computational fluid dynamics (CFD) is used to visualise fluid flow within SCR units and other types of equipment involving phase separators, air intake systems etc. An example is given of use of the commercial CFD code FLUENT to create a full-scale model of an SCR unit so its design could be modified for optimum performance. 1 fig., 1 photo.
Smooth and notched specimens of the bearing steel 100Cr6 (SAE 52100) in a bainitic condition were used to determine the S-N curves under tensile, torsional and combined in- and out-of-phase loading. In the area of high-cycle fatigue, crack initiation was most likely caused by inclusions like Titanium Carbon nitrides or Aluminium Oxides. A micro mechanical model for the crack initiation by inclusions was developed. Another model was developed to describe the influence of these inclusions on the lifetime. A weakest-link model, using the statistical distribution of inclusions and surface flaws, was used to describe the endurance limit. (orig.)
The excellent high temperature strength and thermal conductivity of molybdenum-base alloys provide attractive features for components in advanced magnetic and inertial fusion devices. Refractory metal alloys react readily with oxygen and other gases. Oxidized molybdenum in turn is susceptible to losses from volatile molybdenum trioxide species, MoO{sub 3}(m), in air and the hydroxide, MoO{sub 2}(OH){sub 2}, formed from water vapor. Transport of radioactivity by the volatilization, migration, and re-deposition of these volatile species during a potential accident involving a loss of vacuum or inert environment represents a safety issue. In this report the authors present experimental results on the oxidation, volatilization and re-deposition of molybdenum from TZM in flowing air between 400 and 800 C. These results are compared with calculations obtained from a vaporization mass transfer model using chemical thermodynamic ...
The excellent high temperature strength and thermal conductivity of molybdenum-base alloys provide attractive features for components in advanced magnetic and inertial fusion devices. Refractory metal alloys react readily with oxygen and other gases. Oxidized molybdenum in turn is susceptible to losses from volatile molybdenum trioxide species, (MoO3)m, in air and the hydroxide, MoO2(OH)2, formed from water vapor. Transport of radioactivity by the volatilization, migration, and re-deposition of these volatile species during a potential accident involving a loss of vacuum or inert environment represents a safety issue. In this report we present experimental results on the oxidation, volatilization and re-deposition of molybdenum from TZM in flowing air between 400 and 800°C. These results are compared with calculations obtained from a vaporization mass transfer model using chemical thermodynamic data for vapor ...
Universal Oil Products, Inc. (UOP) of Des Plaines, Illinois has contracted A.E. Roberts & Associates, Inc. (AERA) of Atlanta, Georgia to prepare a sensitivity analysis for the development of the Fluidized-bed Copper Oxide (FBCO) process. As proposed by AERA in September 1991, development of the FBCO process design for a 500 mega-watt (MW) unit was divided into three tasks: (1) Establishment of a Conceptual Design, (2) Conceptual Design, (3) Cost Analysis Task 1 determined the basis for a conceptual design for the 500 megawatt (MW) FBCO process. It was completed by AERA in September of 1992, and a report was submitted at that time {open_quotes}Establishment of the Design Basis for Application to a 500 MW Coal-fired Facility.{close_quotes} Task 2 gathered all pertinent data available to date and reviewed its applicability to the 500 MW FBCO process. Work on this task was carried out on a joint basis by the AERA team members: Roberts & Schaefers worked on the ...
The consequences of converting a facility from brown coal fuel to gas fuel were analyzed by model simulation. Treated were a district heating plant with an output of 700 TJ/yr and minor local heating sources (stoves) at a density of 1 family house per 100 m"2. Emissions of particulate matter, sulfur dioxide, nitrogen oxides, carbon monoxide, and hydrocarbons before and after the conversion are given for the two types of source. Conversion of a major air pollution source to gas fuel would result in a reduction of the contribution of sulfur dioxide emissions of the order of 10"-"4, of particulate matter and carbon monoxide of the order of 10"-"3, and of hydrocarbons of the order of 10"-"2. The decrease will be lowest for nitrogen oxides, viz. about 40%. Analogous data for local heating sources in towns would be 10"-"5 for sulfur dioxide, 10"-"4 for particulate matter, 10"-"3 for carbon monoxide and hydrocarbons, and roughly ...
This report describes the first phase of the AFS/DOE program on mathematical modeling of cupola behavior, covering the period May 19, 1989 to July 19, 1990. The objective of the program is to develop a comprehensive mathematical model of the cupola furnace for on-line and off-line process control and optimization. The work is being carried out by five organizations: Massachusetts Institute of Technology with responsibility for heat transfer and fluid flow modeling, and incorporation of the chemical models being developed by the University of Michigan team. Modern Equipment Company has the responsibility of compiling information on needed sensors for monitoring operation and providing materials data to be used for cupola input. General Motors, Central Foundry Division, is investigating the potential to augment the mathematical models with artificial intelligence programs. Lastly, ...
The aim of this work is to be able to describe transformations, occurring when solids and gases are in non isothermal and non isobaric conditions, with kinetic models. A methodology has been used. Two essential processes have to be taken into account: the germination and the growth. The germs are supposed to be formed (at constant temperature and pressure) in the grains surface with a constant velocity by surface unit, (gamma), called germination surface frequency (number of germs.m{sup -2}.s{sup -1}. The growth velocity is characterized by a growth surface reactivity, (phi) (in mol.m{sup -2}.s{sup -1}). With an appropriate transformation model, it is possible to obtain the variations of (gamma) and (phi) in terms of the temperature and pressure which are then used in the calculation of the velocity in non isothermal and non isobaric conditions. In order to validate the developed method, two reactions have been studied. For the first one, the ...
The finite-volume based commercial CFD-code Fluent was used to simulate the reacting flow in a heavy fuel oil fired laboratory furnace. Both the standard {kappa}-{epsilon} turbulence model and the Reynolds stress model (RSM) were tested. The combustion model was based on the conserved scalar (mixture fraction) and prescribed probability density function approach. The heavy fuel oil droplet trajectories were predicted by solving the momentum equations for the droplets using the Lagrangian treatment. The soot distribution in the furnace was calculated by solving a transport equation for the soot mass fraction. Simple expressions for the soot formation and oxidation rates were employed. The radiation heat transfer equation was solved using the finite volume method. The formation of thermal NO from molecular nitrogen was modeled according to the extended Zeldovich mechanism. Fuel-based ...
Complimentary spectroscopic, microscopic and electrochemical studies were performed to characterise the barrier properties as well as the interface structure of model iron substrates covered with thin plasma polymer films. Cathodic plasma polymers were deposited which show high barrier properties. The metal surface was pre-treated by a reducing or oxidising plasma. This allowed the adjustment of the oxidation state of the interface layer. The interface structure was characterised by means of X-ray photoelectron sputter profiles, infrared spectroscopy and the application of a Kelvin probe. The investigations show that the measured Voltapotential on the plasma polymer surface can be correlated with the oxidation state of the interface. Reducing plasmas lead to an almost oxide free surface. After deposition of the plasma polymer, this reduced state of the oxide is sensitive to ...
This short survey focuses on the main radiation-induced base lesions that have been identified within cellular DNA. For this purpose, sensitive assays that are aimed at measuring a few modifications per 10{sup 7} normal bases were set-up. In that respect high performance liquid chromatography - tandem mass spectrometry (CLHP-MS/MS) was found to be able to single out the formation of 9 oxidized nucleosides and two modified nucleo-bases out of the 70 oxidative base lesions that have been identified in model systems. As a striking result, it was found that in the DNA of {gamma}-irradiated human monocytes, the formamide-pyrimidine derivative of guanine is produced in a higher yield than the ubiquitous 8-oxo-7,8-dihydro-guanine damage, both arising from the same radical precursor. However, relatively high doses of ionizing radiation (> 20 Gy) have to be applied in order to detect an increase in the level of the damage. ...
The environmental problem of ground level ozone is discussed, and the Canadian strategy for dealing with it is explained. Ozone in the troposphere can cause serious health problems in susceptible persons, and is estimated to cause up to $70 million in crop damage per year. The Canadian Council of Ministers of the Environment (CCME) Plan calls for less than 82 ppB by volume of ozone in any one-hour period in all areas of Canada by 2005. Three areas of Canada regularly exceed this value: the Lower Frazer valley in British Columbia, Saint John in New Brunswick, and the Windsor-Quebec corridor along the lower Great Lakes and the St. Lawrence River. Ozone is formed by a photochemical reaction of ammonia gases, nitrogen oxides, hydrogen sulfide or sulfur dioxide. Historically, ozone control has concentrated on controlling hydrocarbon emissions, but to little effect. In most locations close to large cities, ozone production is nitrogen oxide-limited, ...
This dissertation reports on the application of numerical optimization techniques as applied to fuel cell simulation and design. Due to the "multi-physics" inherent in a fuel cell, which results in a highly coupled and non-linear behavior, an experimental program to analyze and improve the performance of fuel cells is extremely difficult. This program applies new optimization techniques with computational methods from the field of aerospace engineering to the fuel cell design problem. After an overview of fuel cell history, importance, and classification, a mathematical model of solid oxide fuel cells (SOFC) is presented. The governing equations are discretized and solved with computational fluid dynamics (CFD) techniques including unstructured meshes, non-linear solution methods, numerical derivatives with complex variables, and sensitivity analysis with adjoint methods. Following the validation of the fuel cell model in ...
The deposit of radioactive corrosion products in the cooling systems of nuclear reactors becomes a serious problem for the personnel of facilities. Crud has an important role in the process of depositing radioactive corrosion products. The main components of crud are hematite, magnetite, nickel ferrite and so on, and the particles of these oxide compounds are distributed in water. Most of the behavior of crud are still not known. As for the mechanism of the production of crud, the Potter-Mann model has been proposed. However, the precipitation process of iron ions in water is unknown. The crud is defined as the particles filtered by 0.45 micrometer millipore filters. However, it is not known whether there are crud particles smaller than this size. The crud particles can be adsorbed on the filters by the surface electrochemical interaction. The adsorption of cations to crud particles was studied. The adhesion of crud particles was investigated ...
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
Neutron resonance interactions with /sup 100/Mo were studied at a time-of-flight facility. The transmission of two oxide samples (97.4% /sup 100/Mo) was measured at a 78.20 m flight path and the neutron capture cross section was measured at 40.12 m. Resonance analyses yielded parameters of 124 resonances. Capture ..gamma..-ray spectra from 11 resolved resonances were measured with a Ge(Li) detector at a 10.45 m flight path. In contrast to neighboring nuclei, partial radiation widths of strong p-wave resonances are not in agreement with valence model predictions.
The development of detailed chemical kinetic reaction mechanisms for analysis of autoignition and knocking of hydrocarbon fuels is described. In particular, kinetic processes of concern for the oxidation of complex hydrocarbon fuel molecules are emphasized. The wide ranges of temperature and pressure which are encountered by end gases in automobile engine combustion chambers result in extreme demands on reaction mechanisms which are intended to describe knocking conditions and predict rates of combustion and ignition. The reactions and chemical species which are most important in each temperature and pressure regime are discussed, and the validation of these reaction mechanisms through comparison with idealized experimental results is described. 53 refs., 8 figs., 5 tabs.
A hydrous oxide film for the application as dielectric film is synthesized by immersion of pure aluminum in hot water. From a Rutherford backscattering analysis, the ratio of aluminum to oxygen atoms was found to be 3:2 in the anodized aluminum oxide film, and 2:1 in the hydrous oxide layer. Anodization of the hydrous oxide layer was more effective for the transition of amorphous anodic oxides to the crystalline aluminum oxides.
Stable boiloff of core water during a severe LWR accident, that is, boiloff driven only by the decay power generated below the water level, is tractable analytically and is relatively insensitive to axial power distribution. As might be expected, calculated accident event times are sensitive to the fidelity of the decay power model. During later stages of boiloff, heat transfer or transport of energy from above the water level to the residual water can result in an unstable condition during which the boiloff rate increases greatly. The unstable boiloff phenomenon illustrates the highly nonlinear influence of core heat transfer during meltdown and emphasizes the great accuracy requirements which attend the modeling of the accident during periods of enhanced heat transfer when significant zirconium oxidation is possible.
Poly(ethylene terephthalate) (PET) powder from waste bottles was degraded at atmospheric pressure in 7--13 M nitric acid at 70--100 C for 72 h, to clarify the mechanism of a feed stock recycling process. Terephthalic acid (TPA) and ethylene glycol (EG) were produced by the acid-catalyzed heterogeneous hydrolysis of PET in nitric acid, and the resulting EG was simultaneously oxidized to oxalic acid. The kinetics of the hydrolysis of PET in nitric acid could be explained by a modified shrinking core model of chemical reaction control, in which the effective surface area is proportional to the degree of unreacted PET, affected by the deposition of the product TPA. The apparent rate constant was inversely proportional to particle size and to the concentration of the nitric acid. The activation energy of the reaction was 101.3 kJ/mol.
The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.
A highly efficient integrated energy conversion system is built based on a methane catalytic decomposition reactor (MCDR) together with a direct carbon fuel cell (DCFC) and an internal reforming solid oxide fuel cell (IRSOFC). In the MCDR, methane is decomposed to pure carbon and hydrogen. Carbon is used as the fuel of DCFC to generate power and produce pure carbon dioxide. The hydrogen and unconverted methane are used as the fuel in the IRSOFC. A gas turbine cycle is also used to produce more power output from the thermal energy generated in the IRSOFC. The output performance and efficiency of both the DCFC and IRSOFC are investigated and compared by development of exact models of them. It is found that this system has a unique loading flexibility due to the good high-loading property of ...
A methane catalytic decomposition reactor-direct carbon fuel cell-internal reforming solid oxide fuel cell (MCDR-DCFC-IRSOFC) energy system is highly efficient for converting the chemical energy of methane into electrical energy. A gas turbine cycle is also used to output more power from the thermal energy generated in the IRSOFC. In part I of this work, models of the fuel cells and the system are proposed and validated. In this part, exergy conservation analysis is carried out based on the developed electrochemical and thermodynamic models. The ratio of the exergy destruction of each unit is examined. The results show that the electrical exergy efficiency of 68.24% is achieved with the system. The possibility of further recovery of the waste heat is discussed and the combined power-heat exergy efficiency is over 80%. (author)
A methane catalytic decomposition reactor-direct carbon fuel cell-internal reforming solid oxide fuel cell (MCDR-DCFC-IRSOFC) energy system is highly efficient for converting the chemical energy of methane into electrical energy. A gas turbine cycle is also used to output more power from the thermal energy generated in the IRSOFC. In part I of this work, models of the fuel cells and the system are proposed and validated. In this part, exergy conservation analysis is carried out based on the developed electrochemical and thermodynamic models. The ratio of the exergy destruction of each unit is examined. The results show that the electrical exergy efficiency of 68.24% is achieved with the system. The possibility of further recovery of the waste heat is discussed and the combined power-heat e...
This study has confirmed large seasonal and daily variations of Rn in soil gas, developed models for the effects of temperature and moisture on air-water Rn partition, inhibited Rn diffusion from wet soil into sparse large air-filled pores and effects of diffusion into bedrock, demonstrated that organic matter is a major host for 226Ra in soils and that organic-bound Ra largely determines the proportion of 222Rn emanated to pore space, shown that in contrast 220Rn is emanated mainly from 224Ra in Fe-oxides, detected significant disequilibrium between 226Ra and 238U in organic matter and in some recent glacial soils, demonstrated by computer models that air convection driven by temperature differences is expected in moderately permeable soils on hillsides.
This study has confirmed large seasonal and daily variations of Rn in soil gas, developed models for the effects of temperature and moisture on air-water Rn partition, inhibited Rn diffusion from wet soil into sparse large air-filled pores and effects of diffusion into bedrock, demonstrated that organic matter is a major host for 226Ra in soils and that organic-bound Ra largely determines the proportion of 222Rn emanated to pore space, shown that in contrast 220Rn is emanated mainly from 224Ra in Fe-oxides, detected significant disequilibrium between 226Ra and 238U in organic matter and in some recent glacial soils, demonstrated by computer models that air convection driven by temperature differences is expected in moderately permeable soils on hillsides.
The analysis described demonstrates the use of benefit/cost sensitivity analysis in examining the wide range of potential damages and savings associated with converting oil-fired electric utility boilers to burn coal in Florida. This model, for the first time incorporates, in quantitative terms, environmental economic externalities into a benefit/cost ratio sensitivity analysis framework. Five different dose-response estimates of morbidity and mortality costs, property devaluation, and willing-to-pay estimates are used in combination with four acid rain dose-response models to estimate the net present worth of externality costs. The model estimates the net present worth of benefits by incorporating into a dynamic framework all relevant construction, O + M, and fuel costs of converting an electrical generation facility from using oil to coal. These benefits of fuel savings are then weighted against various combinations of ...
Combustion scientists are primarily concerned with the fuels most often burned as energy sources (coal, petroleum products, and natural gas), with the goal of learning to burn them as efficiently, intensely, and cleanly as possible. Discovering those slight rearrangements of chemical bonds that together account for the net chemical transformation is the key to understanding how combustion proceeds. Once these reactions have been defined, the chemist can determine the rate coefficient of each reaction as a function of temperature and assemble the information into flame models. The computer programs that use these models to predict experimental results combine two sets of equations describing (1) the diffusive and reactive rates of change in concentration of all the molecules in the flame and (2) the flow of the reacting gases. Although the details of hydrocarbon-flame models are still disputed, many of their general features ...
Fuel irradiation leads to a swelling resulting from the formation of gaseous (Kr, Xe) or solid fission products which are found either in solution or as solid inclusions in the matrix. This phenomena has to be evaluated to be taken into account in fuel cladding Interaction. Fuel swelling was studied as a function of burn up by measuring the corresponding cell constant evolution by X-Ray diffraction. This study was realized on Mixed Oxide Fuels (MOX) irradiated in a Pressurized Water Reactor (PWR) at different burn-up for 3 initial Pu contents. Lattice parameter evolutions were followed as a function of burn-up for the irradiated fuel with and without an annealing thermal treatment. These experimental evolutions are compared to the theoretical evolutions calculated from the hard sphere model, using the fission product concentrations determined by the APPOLO computer code. Contribution of varying parameters influencing the unit cell value is ...
Neuronal cell death induced by oxidative stress is correlated with numerous neurodegenerative diseases, including Alzheimer's disease (AD), Parkinson's disease (PD), and stroke. The causes of sporadic forms of age-related neurodegenerative diseases are still unknown. Recently, a correlation between paraquat exposure and neurodegenerative diseases has been observed. Paraquat, a nonselective herbicide, was once widely used in North America and is still routinely used in Taiwan. We have used differentiated Human Neuroblastoma (SHSY-5Y) cells as an in vitro model to study the mechanism of cell death induced by paraquat. We observed that paraquat-induced oxidative stress in differentiated SHSY-5Y cells as indicated by an increase in the production of cellular reactive oxygen species (ROS). Furthermore, apoptosis was evident as indicated by cellular and nuclear morphology and DNA fragmentation. Interestingly, pretreatment of ...
By means of an audio frequency plasma polymerisation ultra-thin gradient plasma polymer layers were deposited on zinc and zinc-coated iron. The aim was to generate an interfacial polymeric layer which bonds to an oxidised metal as well as to a subsequently applied organic coating and acts as an interfacial barrier layer for ions and water. Surface modifications were done in an in situ plasma cell with infrared reflection absorption spectroscopy (IRRAS). The zinc surface was first activated by an oxygen plasma to provide a freshly oxidised and contamination free oxide surface. The intermediate stages of the surface reactions could be revealed. Carbon dioxide molecules as oxidation products adsorbed on the growing zinc oxide and were desorbed at a later stage. An organosilicon plasma polymer was deposited directly on top of the oxide layer from a hexamethyldisilane (HMDS) plasma. Afterwards a cyclohexene ...
The oxidative stress theory of aging predicts that manipulations that alter oxidative stress/damage will alter aging. The gold standard for determining whether aging is altered is lifespan,...Full Text Available
Bi-U mixed oxides were synthesized by two methods and characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The samples were tested for the catalytic oxidation of carbon monoxide by oxygen. A stepwise redox mechanism consistent with the kinetic results is proposed. (orig.).
To improve mirrors coating, we have modeled sputtering of binary oxide targets using TRIM code. First, we have proposed a method to calculate TRIM input parameters using on the one hand thermodynamic cycle and on the other hand Malherbe`s results. Secondly, an iterative processing has provided for oxide steady targets caused by ionic bombardment. Thirdly, we have exposed a model to get experimental sputtering yields. Fourthly, for (Ar - SiO{sub 2}) pair, we have determined that steady target is a silica one. A good agreement between simulated and experimental yields versus ion incident angle has been found. For (Ar - Ta{sub 2} O{sub 5}) pair, we have to introduce preferential sputtering concept to explain discrepancy between simulation and experiment. In this case, steady target is tantalum monoxide. For (Ar - Ta+O{sub 2}) pair, tantalum sputtered by argon ions in reactive oxygen atmosphere, we have to ...
To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and ...
Chemical oxidation is a treatment technology that uses powertul chemical oxidizers to destroy organic contaminants. Typical oxidizers used in chemical oxidation processes include ozone, hydrogen peroxide, chlorine, and potassium permanganate. The chemical reaction products are usually simple organic compounds, such as carboxylic acids, and/or inorganic compounds, such as carbon dioxide, water, and simple inorganic complexes (e.g., chloride salts, in the case of chemical oxidation treatment of chlorinated solvents).
Activation reactions of coal reject-derived char (CRC) with CO{sub 2}, H{sub 2}O and air are experimentally studied using a thermogravimetric analysis technique. The experimental kinetic data are treated via kinetic data unification based on the half-time, and the intrinsic rate constants are extracted by the modified Arrhenius plot method. The effect of structural evolution on the overall rate changes is modelled with a modified random pore model and percolation model taking into account the ash content of the coal reject char. It is found that the relative reaction rates for the reaction pairs CO{sub 2}-CRC, H{sub 2}O-CRC and air-CRC are at an increasing order of sequence at a given temperature. The effect of gaseous pressure on the reaction rate is shown to be significant for CO{sub 2}-CRC and H{sub 2}O-CRC reactions. It has shown that both models can predict well the maximum rate and the conversion ...
High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a ...
The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence ...
Glass produced during the Purex 4 campaigns of the Integrated Defense Waste Processing Facility (DWPF) Melter System (IDMS) and the 774 Research Melter contained a lower fraction of sludge components than targeted by the Product Composition Control System (PCCS). Purex 4 glass was more durable than the benchmark (EA) glass, but less durable than most simulated SRS high-level waste glasses. Also, Purex 4 glass was considerably less durable than predicted by the algorithm which will be used to control production of DWPF glass. A melter run was performed using the 774 Research Melter to determine if the initial PCCS target composition determined for Purex 4 would produce acceptable glass whose durability could be accurately modeled by Hydration Thermodynamics. Reagent grade oxides and carbonates were added to Purex 4 melter feed stock to simulate a higher sludge loading. Each canister of glass produced was sampled and the composition, ...
Glass produced during the Purex 4 campaigns of the Integrated DWPF Melter System (IDMS) and the 774 Research Melter contained a lower fraction of sludge components than targeted by the Product Composition Control System (PCCS). Purex 4 glass was more durable than the benchmark (EA) glass, but was less durable than most other simulated SRS high-level waste glasses. Further, the measured durability of Purex 4 glass was not as well correlated with the durability predicted from the DWPF process control algorithm, probably because the algorithm was developed to predict the durability of SRS high-level waste glasses with higher sludge content than Purex 4. A melter run, designated Purex 4 Remediation, was performed using the 774 Research Melter to determine if the initial PCCS target composition determined for Purex 4 would produce acceptable glass whose durability could be accurately modeled by the DWPF glass durability algorithm. Reagent grade ...
On-board reforming of liquid fuels to hydrogen for use in proton exchange membrane (PEM) fuel cell electric vehicles (FCEVs) has been the subject of numerous investigations. In many respects, liquid fuels represent a more attractive method of carrying hydrogen than compressed hydrogen itself, promising greater vehicle range, shorter refilling times, increased safety, and perhaps most importantly, utilization of the current fuel distribution infrastructure. The drawbacks of on-board reformers include their inherent complexity [for example a POX reactor includes: a fuel vaporizer, a reformer, water-gas shift reactors, a preferential oxidation (PROX) unit for CO cleanup, heat exchangers for thermal integration, sensors and controls, etc.], weight, and expense relative to compressed H{sub 2}, as well as degraded fuel cell performance due to the presence of inert gases and impurities in the reformate. Partial oxidation (POX) of automotive fuels is ...
As part of the 1999 NARSTO Northeast Oxidant and Particulate Study (NE-OPS) field campaign, the DOE G-1 aircraft sampled trace gases and aerosols in and around the Philadelphia metropolitan area. Twenty research flights were conducted between July 25 and August 11. The overall goals of these flights were to obtain a mechanistic understanding of O(sub 3) production; to characterize the spatial and temporal behavior of photo-oxidants and aerosols; and to study the evolution of aerosol size distributions, including the process of new particle formation. Within the NE-OPS program, other groups provided additional trace gas, aerosol, and meteorological observations using aircraft, balloon, remote sensing, and surface based instruments (Phillbrick et al., 2000). In this article we provide an overview of the G-1 observations related to O(sub 3) production, focusing on the vertical distribution of pollutants. Ozone production rates are calculated using ...
We analyze the impact of trap states in the oxide layer of a superconducting tunnel junctions, on the fluctuation of the Josephson critical current, thus on coherence in superconducting qubits. Two mechanisms are usually considered: the current blockage due to repulsion at the occupied trap states, and the noise from electrons hopping across a trap. We extend previous studies of noninteracting traps to the case where the traps have on-site electron repulsion inside one ballistic channel. The repulsion not only allows the appropriate temperature dependence of 1/f noise, but also is a control to the coupling between the computational qubit and the spurious two-level systems inside the oxide dielectric. We use second order perturbation theory which allows to obtain analytical formulae for the interacting bound states and spectral weights, limited to small and intermediate repulsions. Remarkably, it still reproduces the main features of the ...
Primary objective was to investigate the effects of pore structure on capacity of porous metal oxides for removal of SO[sub 2] from power plant fuel gas and H[sub 2]S from hot coal gas. During this period, a comparative study was carried out on the direct reaction with H[sub 2]S and SO[sub 2] of the three limestones used as CaO precursors: Greer limestone, Georgia marble, and Iceland spar calcite. Sulfation was carried out at 750 and 850 C in a thermogravimetric analysis system under simulated high pressure (enough CO[sub 2] to prevent decomposition of CaCO[sub 3]). Results are presented as conversion vs time graphs. Mercury penetration and gas adsorption were used to analyze the structure. Activation energies and effective diffusivities were determined. A variable diffusivity shrinking-core model was used to analyze the data. In the future, this limestone study will be completed, and a study on supported CuO sorbent will be started.
The oxidation of CO over a Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied by cyclic injection of CO and O{sub 2} pulses under CO and O{sub 2} pressures of 2 and 1 kPa, respectively, at temperatures of 330-650 K. A boundary reaction model yielded kinetic parameters in agreement with the results of published low-pressure studies. For CO{sub 2} formation from O{sub 2}(g) + (CO){sub ad}, CO desorption was the most important step and showed multipeak characteristics and a low activation energy (10 kJ/mol) for the boundary reaction was found. CO{sub 2} formation from O{sub 2}(g) + (CO) as well as from CO(g) + (O){sub ad} resulted from boundary reaction at oxygen island. A reaction mechanism was proposed to account for kinetics observed and interpret the varying observations noted in low-pressure studies in terms of diffusion-disguised kinetics.
Modelization of crack propagation and theoretical prediction of rupture are the two main objectives of researchers in stress corrosion cracking. Nevertheless, to reach this aim, the behavior of the passive film which appears spontaneously on the substrate in contact with an environment has to be known. This structural and mechanical characterization is all the more difficult because the number of parameters is important: crystallinity rate, defects concentration, thickness (about a few nanometers), electric field, chemical composition (a lot of oxides are present), peeling layers (atomic structure for example) and some hypothesis can be made about their multi-layer structure, their chemical composition or their epitaxial character... Passive films formed on 316L or 304L stainless steels in different aqueous solutions (in ambient air, in MgCl{sub 2} at 117 deg. C...) have been studied and some important remarks about their mechanical properties ...
Modelization of crack propagation and theoretical prediction of rupture are the two main objectives of researchers in stress corrosion cracking. Nevertheless, to reach this aim, the behavior of the passive film which appears spontaneously on the substrate in contact with an environment has to be known. This structural and mechanical characterization is all the more difficult because the number of parameters is important: crystallinity rate, defects concentration, thickness (about a few nanometers), electric field, chemical composition (a lot of oxides are present), peeling layers (atomic structure for example) and some hypothesis can be made about their multi-layer structure, their chemical composition or their epitaxial character... Passive films formed on 316L or 304L stainless steels in different aqueous solutions (in ambient air, in MgCl_2 at 117 deg. C...) have been studied and some important remarks about their mechanical properties are ...
The effect of adding hydrogen to methane as a fuel for spark ignited engines has been extensively investigated. Both the possibility of adding a limited amount of hydrogen as well as equal amounts of hydrogen and carbon dioxide to natural gas has been investigated. A 10 vol% addition of hydrogen to the natural gas caused a reduction in UHC of approximately 40%, and an increase in efficiency of approximately three percentage points at the test engine. It is unknown if the gain is representative for large engines. Similar results for UHC reduction and efficiency were obtained for combined hydrogen and carbon dioxide addition. The carbon dioxide was added by exhaust gas recirculation. However, the price of hydrogen, makes this idea uneconomical even when carbon dioxide is readily available through recirculation of engine exhaust. Adiabatic prereforming may be used to convert natural gas into methane, hydrogen and carbon dioxide in order to generate hydrogen and at the same time increase ...
We provide a detailed overview of an ongoing, multinational test program that is developing aerosol data for some spent fuel sabotage scenarios on spent fuel transport and storage casks. Experiments are being performed to quantify the aerosolized materials plus volatilized fission products generated from actual spent fuel and surrogate material test rods, due to impact by a high energy density device, HEDD. The program participants in the U.S. plus Germany, France, and the U.K., part of the international Working Group for Sabotage Concerns of Transport and Storage Casks, WGSTSC have strongly supported and coordinated this research program. Sandia National Laboratories, SNL, has the lead role for conducting this research program; test program support is provided by both the U.S. Department of Energy and Nuclear Regulatory Commission. WGSTSC partners need this research to better understand potential radiological impacts from sabotage of nuclear material shipments and storage casks, and ...
The suitability of the turbulent combustion flamelets model in order to predict the index of NO{sub x} production in turbulent flames of hydrogen diffusion is analyzed. In the flamelet approach, the turbulent flame is equivalent to a group of laminar flames submitted to a mechanical stretching which generates a chemical disequilibrium. This effect can be described by the stretching or by the scalar dissipation ratio. A numerical modeling is performed in order to evaluate the advantages of both approaches and to compare the behaviour of the NO{sub x} emission index with the experiments of Chen and Driscoll. This study shows that predictions of NO{sub x} emission indexes have a correct behaviour with respect to the Damkoehler number only when the scalar dissipation ratio is used as a parameter to describe the chemical state outside equilibrium. Predictions of the flamelet models are improving when the Damkoehler number ...
Combustion of extremely fuel-rich ({phi}=4) methane/air mixtures at elevated pressures is investigated as a potential means to generate molecular hydrogen by non-catalytic partial oxidation. This system is investigated both computationally and experimentally. The computations use a perfectly-stirred reactor model and an explicit methane cool-flame mechanism to investigate the effects of reactor parameters on reaction time and product composition. Under adiabatic conditions, such mixtures are predicted to autoignite at low temperatures {approx}700 K for pressures exceeding 8.5 atm. Above 15 atm, conversion to products is complete in roughly 1 s. The dependence of reaction time and hydrogen yield is investigated as a function of inlet temperature, system pressure, and flame equivalence ratio. Actual product yields are measured in a tube reactor facility, and many of the predictions of the model, including long relaxation ...
The super simulator 'SAMPSON' has been developed to show that there exist certain safety margins for light water reactors under hypothetical severe accidents and to investigate realistic measures of accident management by simulating accidents with a parallel computer. Heat-up of fuel rods and release of fission products from fuels are important factors to evaluate source terms. Models for fuel rod heat-up, hydrogen production due to cladding oxidation and cladding deformation and failure in the core region have been developed in the fuel rod heat-up analysis module. Fuel temperatures were calculated by solving the heat conduction equation. The calculated results for fuel temperature and hydrogen production were compared with CORA-13 experiment results. The comparisons showed prediction capability for the heat-up of fuel rods. The fission product release analysis module incorporates with models for fission product transport ...
This work was carried out to understand the behavior of the solid and gas phases in a CFB riser. Only the riser is modeled as a straight pipe. A model with linear algebraic approximation to solids viscosity of the form, {musubs} = 5.34{epsisubs}, ({espisubs} is the solids volume fraction) with an appropriate boundary condition at the wall obtained by approximate momentum balance solution at the wall to acount for the solids recirculation is tested against experimental results. The work done was to predict the flow patterns in the CFB risers from available experimental data, including data from a 7.5-cm-ID CFB riser at the Illinois Institute of Technology and data from a 20.0-cm-ID CFB riser at the Particulate Solid Research, Inc., facility. This research aims at modeling the removal of hydrogen sulfide from hot coal gas using zinc oxide as the sorbent in a circulating fluidized bed and in the process ...
Oxidation of propylene with oxygen, air and a mixture of nitrogen?oxygen in a barrier discharge is investigated. The selectivity towards formation of propylene oxide in pure oxygen is shown to be as high as 45 wt% and the propylene conversion ratio is found to be 12.9 wt%. In the oxidation with air, the propylene oxide selectivity is 23 wt%, while the conversion is 7.5 wt%. The values of propylene conversion and selectivity towards formation of propylene oxide in a barrier discharge are consistent with those obtained by the thermocatalytic methods for production of propylene oxide.
The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure range of 1 to 10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the ...
The aim of the work in this thesis is to investigate the convective and diffusive transport in the TM chemistry transport model, and to investigate some aspects of the consequences for NOx. The large inaccuracy and uncertainty in the description of processes like convection and turbulent diffusion, the strong dependence of the radiative forcing of ozone on its vertical distribution, and the strong dependence of the ozone production on the distribution of NOx, are the main motivation. The availability of the ERA-40 data, where convective data and vertical diffusion coefficients are archived, allows a study of the effect of different convective mass flux sets, and different vertical diffusion coefficients on the model-simulated distribution of tracers. In this thesis the following questions are addressed : (1) How large is the sensitivity of the (model simulated) distribution of ozone and nitrogen oxides ...
In order to avoid the use of catalysts in the process of auto-thermal reforming, it is possible to adopt a running at high temperature. In this study are presented the results of simulations of an auto-thermal/recuperator hybrid reforming system; these results are obtained with the oxidationmodel of alkanes developed by Ranzi and Faravelli. An isothermal configuration at high temperature improves the hydrogen yield and avoids the formation of soots. The analysis of the powers to be furnished to assure such an experimental mode, and the global approach of the fuel cell system show that the management of the heat exchanges is a key parameter in this process. (O.M.)
The future use of single-molecule magnets in applications will require the ability to control and manipulate the spin state and magnetization of the magnets by external means. There are different approaches to this control, one being the modification of the magnets by adsorption of small ligand molecules. In this paper we use iron phthalocyanine supported by an Au(111) surface as a model compound and demonstrate, using x-ray photoelectron spectroscopy and density functional theory, that the spin state of the molecule can be tuned to different values (S #approx# 0, 1/2, 1) by adsorption of ammonia, pyridine, carbon monoxide or nitric oxide on the iron ion. The interaction also leads to electronic decoupling of the iron phthalocyanine from the Au(111) support. (fast track communication)
Treatment of coal or coconut shell activated carbons with either phosgene or chlorine at 180{degree}C followed by washing with methanol or water results in chlorinated carbons with very similar pore structures to their precursors. Water adsorption experiments show that the modified materials are relatively hydrophobic, presumably as a result of replacement of oxygen-containing surface groups by chlorine. Adsorption of the model hydrophobic vapour chloropicrin from humid air is usually better for the modified carbons which, unlike the controls, do not appear to be subject to degradation in performance on ageing in a humid atmosphere. The stability of the modified carbons is probably a consequence of the chlorination of those sites on the control carbons that are prone to ready oxidation or hydroxylation. 1 tab., 2 figs., 17 refs.
In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ("1"2C"1"6O/"1"3C"1"8O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO_2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate.
Recent progress in yttrium-based oxide high-temperature superconductors has enabled the production of a large diameter bulk with a strong flux-pinning force. A combination of this superconductor and a permanent magnet makes it feasible to fabricate a noncontact, non-controlled superconducting magnetic bearing with a very small rotational loss, applicable to a flywheel energy storage system. A conceptual design of an 8 MWh flywheel energy storage system using the new bearing has been developed, based on measured data on a miniature bearing model, which proved to be potentially capable of achieving a high energy storage efficiency of 84 pc. A 100 W h-class experimental system was then built, which attained a high revolution rate of 17000 rpm, with a rotational loss of about 0.6 W. (authors). 2 refs., 7 figs., 3 tabs.
Neutron resonance interactions with "1"0"0Mo were studied at a time-of-flight facility. The transmission of two oxide samples (97.4% "1"0"0Mo) was measured at a 78.20 m flight path and the neutron capture cross section was measured at 40.12 m. Resonance analyses yielded parameters of 124 resonances. Capture #gamma#-ray spectra from 11 resolved resonances were measured with a Ge(Li) detector at a 10.45 m flight path. In contrast to neighboring nuclei, partial radiation widths of strong p-wave resonances are not in agreement with valence model predictions.
The optical and nonlinear optical properties of colloidal solutions of silver obtained by laser ablation in water and ethanol are studied. It is shown that freshly prepared colloids experience a full or partial sedimentation by changing their nonlinear optical properties. Aqueous colloids undergo a partial sedimentation and their nonlinear optical absorption changes to nonlinear optical transmission. The obtained results are interpreted using the Drude model for metal particles taking the particle size into account and can be explained by the sedimentation of larger silver particles accompanied by the formation of a stable colloid containing silver nanoparticles with a tentatively silver oxide shell. The characteristic size of particles forming such a stable colloid is determined and its optical nonlinearity is estimated.
Lebers hereditary optic neuropathy (LHON), the most frequent mitochondrial disorder, is mostly due to three mitochondrial DNA (mtDNA) mutations in respiratory chain complex I subunit genes: 3460/ND1, 11778/ND4 and 14484/ND6. Despite considerable clinical evidences, a genetic modifying role of the mtDNA haplogroup background in the clinical expression of LHON remains experimentally unproven. We investigated the effect of mtDNA haplogroups on the assembly of oxidative phosphorylation (OXPHOS) complexes in transmitochondrial hybrids (cybrids) harboring the three common LHON mutations. The steady-state levels of respiratory chain complexes appeared normal in mutant cybrids. However, an accumulation of low molecular weight subcomplexes suggested a complex I assembly/stability defect, which was ...
The development of new efficient afterglow phosphors is currently hampered by a limited understanding of the persistent luminescence mechanism. Radioluminescence (RL) and x-ray absorption measurements on the persistent phosphor SrAl2O4:Eu,Dy were combined to reveal possible valence state changes for the rare earth (co)dopants. Traps in the phosphor material are quickly filled when exposing thermally emptied SrAl2O4:Eu,Dy powder to x rays. On the same time scale a partial oxidation of Eu2+ to Eu3+ is observed by x-ray absorption near-edge spectroscopy (XANES), while for the trivalent dysprosium the valence state remains unchanged. The impact of these observations on the recently proposed models for persistent luminescence is discussed.
In this paper, 0.75Pb(Fe2/3W1/3)O3-0.25PbTiO3-0.15 wt% MnO (0.75PFW-0.25PT-0.15 wt% MnO) ceramics are synthesized by two different methods, the conventional direct oxide synthesized (DS) method and two-step indirect synthesized (IS) method. The low-field dielectric responses are investigated by using the empirical law, the Curie-Weiss law, the modified-Landau theory and the spin-glass model. Due to the IS method, the lattice structure and the grain structure of the samples are changed. Furthermore, the dielectric properties are evidently modified. It is suggested that the ordering degree of B-site cations is enhanced by using the IS synthesized method.
Passive films formed on Alloy 690 in different pH solutions at high temperatures were studied by potentiodynamic polarization, Auger electron spectroscopy, thermodynamic diagrams and the Mott-Schottky relation. The chemical compositions and electronic structures of the passive films were found to be strongly pH-dependent. In alkaline solutions, a secondary passivation was clearly observed on potentiodynamic polarization curves. The passive films were a mixture of Cr{sub 2}O{sub 3} and FeCr{sub 2}O{sub 4} below the flat band potential of nickel oxide and were NiFe{sub 2}O{sub 4} above this potential. Electronic structure models, describing the electrochemical properties of the passive films, are proposed and discussed.
Passive films formed on Alloy 690 in different pH solutions at high temperatures were studied by potentiodynamic polarization, Auger electron spectroscopy, thermodynamic diagrams and the Mott-Schottky relation. The chemical compositions and electronic structures of the passive films were found to be strongly pH-dependent. In alkaline solutions, a secondary passivation was clearly observed on potentiodynamic polarization curves. The passive films were a mixture of Cr2O3 and FeCr2O4 below the flat band potential of nickel oxide and were NiFe2O4 above this potential. Electronic structure models, describing the electrochemical properties of the passive films, are proposed and discussed.
Abstract Hybrid power plants consisting of a solid oxide fuel cell (SOFC) and a gas turbine show high electrical efficiencies, however require pressurisation of the SOFC to several bar. This paper presents a theoretical investigation of the pressure influence on SOFC performance and durability. A two-dimensional elementary kinetic model is used to predict the performance of a single cell in the pressure range of 1-20-bar. The influence of pressure on thermodynamics, reaction kinetics, porous electrode diffusion, channel transport and efficiency is assessed. It was found that polarisation resistance decreases with increasing pressure due to increased diffusion through porous electrodes and a higher electrode surface coverage with reactant species. Furthermore, open-circuit voltage increases...
This paper presents a reformer prototype for the production of the necessary H{sub 2} to supply a 5 kW PEMFC and its first results. The fuel processor consists of an OSR and a WGS and a PROX reactors. The design of the system was carried out with a one-dimensional model. The mixture chamber was specially studied with a CFD code (Fluent), taking into account the effect of fuel evaporation and the cool flame process. The aim of the designed facility is to be able of characterising each component and controlling each working parameter. Eventually, using diesel as fuel, results from the mixture chamber, OSR, WGS and PROX reactors are presented. It also includes conclusions and future works. (authors)
It is hypothesized that the good performance of Alloy 800 in steam generator service is due to its relative immunity to two distinct mechanisms of stress corrosion cracking; the argument also applies to intergranular corrosion. One mechanism operates in the high-nickel region (Alloy 600 and nearby model alloys) and is due to internal intergranular oxidation. The other operates in the low-nickel (stainless steel) region and is due to de-alloying of Fe and/or Cr. This latter mechanism may, under special conditions, operate in high-Ni, high-Cr alloys such as 690. Some essential features of the de-alloying mechanism are demonstrated using strong caustic solutions, and the prospect of extending this approach to dilute high-temperature environments is discussed. (author)
A series of cyclic voltammetry, chronoamperometry and electrochemical impedance experiments have been carried out in order to investigate the effect of cathode composition and porosity on the electrochemical characteristics of strontium-doped lanthanum, praseodymium and gadolinium cobaltite cathodes. The impedance responses at different electrode potentials of the half cell and symmetric single cell setups are compared and analyzed by the equivalent circuit modeling method. The deconvolution of impedance spectra for single cell cathode and anode reactions contributions based on the results of simultaneous analysis of half cells and symmetric single cells has been made by differential impedance real part vs. ac frequency plot analysis method. Noticeable influence of cathode chemical composition, meso-porosity and macro-porosity on the electrochemical activity of the oxygen electroreduction has been demonstrated. Seeming activation energy values have been calculated ...
Ozone has in recent years been increasingly investigated for its potential use in the control of insect pests of stored cereals. Ozone is a powerful oxidizing agent that can react directly, or via production of reactive oxygen species, with proteins, DNA and double bonds of polyunsaturated fatty acids (PUFA). The aim of the present study was to investigate the mode of action in ozone toxicity using the red flour beetle, Tribolium castaneum (Herbst), as a relevant model. Transcription of focal genes thought to be involved in protection against ozone, and repair of cellular damage caused by ozone exposure, was studied together with the composition of storage lipid fatty acids and membrane phospholipid fatty acids in order to detect lipid peroxidation. Contrary to expectations, transcription ...
Polyacrylonitrile (PAN)-based carbon fabric (CF) was modified with strong HNO3 oxidation and then introduced into polyimide (PI) composites. The friction and wear properties of the carbon fabric reinforced polyimide composites (CFRP), sliding against GCr15 stainless steel rings, were investigated on an M-2000 model ring-on-block test rig under dry sliding. Experimental results revealed that the carbon fiber surface treatment largely reduced the friction and wear of the CFRP. Compared with the untreated ones, the surface-modified CF can enhance the tribological properties of CFRP efficiently due to the improved adhesion between the CF and the PI matrix. Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) study of the carbon fiber surface showed that the fiber surfa...
Under operational conditions in nuclear power plants, the carbon steel components of the primary and secondary circuits react with high temperature cooling agent forming several iron oxides and oxyhydroxides. These deposits can result in tubes' constrictions, pitting and intergranular corrosion and finally to heat transfer reducing and increasing of radiation fields around the circuits, as well. The descaling process involves the chemical dissolution of the corrosion deposits by means of diluted organic acidic solutions containing usually a carboxylic acid, a reductant and one or more corrosion inhibitors. To evaluate the removing rates of these superficial films two types of methods were used, the gravimetric and potentiodynamic techniques. By correlating the experimental results, we established the chemical composition of descaling solution and two models of mechanisms applicable to our specific conditions. (authors)
Nanoscale yttrium?barium?copper oxide (Y2BaCuO5, Y211) particles were synthesized using the emulsion method and the solution method. The basic water-in-oil (w/o) emulsion system consisted of n-octane (continuous oil phase), cetyltrimethylammonium bromide (cationic surfactant), butanol (cosurfactant) and water. The composition of the emulsion system was varied and characterized by measuring the conductivity of the solutions and droplet size. The droplet size of emulsion was determined by using the dynamic light scattering method. The water content, cosurfactant content, and surfactant/n-octane ratio affected the droplet size which was in the range of 3?8?nm, and hence the w/o emulsion system was referred to as a nano-emulsion system. A model was used to verify the droplet size. The influenc...
The CERL Code was developed to describe the solution chemistry of the water on the steam generating side of PWR reactors. It is designed to calculate the equilibrium species distribution resulting from the interaction of impurities, corrosion products, and additives in the aqueous solution. It calculates the extent of ion-ion interactions, the precipitation of insoluble species and the amount of solute that partitions into the vapor phase when some of the water evaporates. This knowledge of the bulk phase equilibrium distribution of species, especially the pH should be useful in describing the corrosion processes at the solid liquid boundary. The code does not calculate any changes in oxidation states or any rates of reaction. Therefore, it is incapable of calculating the actual corrosion rates. It is anticipated that it will be used as a subprogram of a larger program that will include the redox reactions and the rates of the reactions. The purpose of the code at ...
4-Methylcoumarins that possess two hydroxyl groups ortho to each other in the benzenoid ring have shown to have excellent antioxidant and radical-scavenging properties in different experimental models. Furthermore, they cannot be metabolized by the liver P450 monoxygenases and thus cannot form 3,4-coumarin epoxides, which are believed to be mutagenic. Herein, we present a study on the structure activity relationship of eight synthetic 4-methylcoumarins, carried out by employing a series of different chemical cell-free tests. These compounds were tested by means of three assays involving one redox reaction with the oxidant (DPPH assay, ABTS+ assay and FRAP). Other assays were employed to evaluate the antioxidant properties of the coumarins under investigation against NO, O2- and HClO, which...
Rhodium (Rh) is a critical component of current automotive three-way catalysts (TWCs), particularly with regard to NO{sub x} and CO conversion at rich and stoichiometric air-fuel ratios (A/F). Rh supported on CeO{sub 2} was active for NO{sub x} and CO conversions but could be deactivated easily by high temperature aging. The cause of the deactivation is ascribed to the sintering of CeO{sub 2}. ZrO{sub 2} incorporation into CeO{sub 2} is reported to have high thermal durability in terms of oxygen storage capacity (OSC). There has been no report showing direct experimental evidence that Rh-loaded on CeO{sub 2}-ZrO{sub 2} mixed oxides induced effects on TWC performance improvement in the actual automotive exhaust. In the present paper, the Rh-CeO{sub 2} interaction contributing to NO{sub x} reduction and the catalytic behavior of Rh-loaded CeO{sub 2}-ZrO{sub 2} mixed oxide is addressed. Incorporating CeO{sub 2}-ZrO{sub 2} into a catalyst offered ...
An investigation of the mechanism of the oxidation and ammoxidation of propylene was made. The products of the above reactions were acrylonitrile and acrolein for ammoxidation and oxidation, respectively. Also, the ammoxidation and oxidation of allyl alcohol, allyl amine, and their allylic deuterium substituted analogues was studied. It was concluded that oxidation and ammoxidation of propylene have the same rate determining step. Other conclusions about the reaction intermediates were also made.
The electrochemical oxidation as a method to destroy drug residues like Aspirin {sup trademark}, tetracycline or gentamicin in water was investigated with C-Anode (modified by manganese oxides) and Pt Anode. The mechanism of Aspirin {sup trademark} and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general the biological availability increases with progressive oxidation of the antibiotics. (orig.)
Hydrothermal oxidation (HTO) is a promising technology for the treatment of aqueous-fluid hazardous and mixed waste streams. Waste streams identified as likely candidates for treatment by this technology are primarily aqueous fluids containing hazardous organic compounds, and often containing inorganic compounds including radioisotopes (mixed wastes). These wastes are difficult and expensive to treat by conventional technologies (e.g. incineration) due to their high water content; in addition, incineration can lead to concerns related to stack releases. An especially attractive potential advantage of HTO over conventional treatment methods is the total containment of all reaction products within the overall system. The potential application of hydrothermal oxidation (HTO) technology for the treatment of DOE hazardous or mixed wastes has been uncertain due to concerns about safe and efficient operation of the technology. In principle, aqueous ...
The objective of this work is to improve the process for CO{sub 2} capture by alkanolamine absorption/stripping by developing an alternative solvent, aqueous K{sub 2}CO3 promoted by piperazine (PZ). Pilot plant testing was performed in a 16.8-inch ID absorber and stripper with recirculation of air and CO{sub 2}. Three solvents (7 m MEA, 5 m K{sup +}/2.5 m PZ, and 6.4 m K{sup +}/1.6 m PZ) were tested in four campaigns with three different absorber packings. Pilot plant testing established that 5 m K{sup +}/2.5 m PZ requires two times less packing than 7 m MEA and three times less packing than 6.4 m K{sup +}/1.6 m PZ. A rigorous model of the thermodynamics and mass transfer was developed in the RateSep{trademark} block of AspenPlus{reg_sign}. The double matrix stripper reduces energy consumption by 5 to 15%. The best K{sup +}/PZ solvent, 4 m K{sup +}/4 m PZ, and the best process configuration, double matrix stripper with a double intercooled absorber, requires ...
The widely accepted oxidative stress theory of aging postulates that aging results from accumulation of oxidative damage. Surprisingly, data from the longest-living rodent known, naked mole-rats [MRs;...Full Text Available
Background. The Free Radical Theory of Aging mechanistically links oxidative stress to aging. Okinawa has among the world's longest-lived populations but oxidative stress in this...Full Text Available
Oxidative stress occurs when the level of prooxidants exceeds the level of antioxidants in cells resulting in oxidation of cellular components and consequent loss of cellular function. Oxidative...Full Text Available
1. Nitric oxide generation is important in the regulation of resistance vessel tone. Until now, however, there has been no evidence of such a role for basal generation of nitric oxide in the skin microcirculation...Full Text Available
The catalytic effects of copper-aluminium-magnesium oxides in the oxidative coupling of phenylethyne is described. The importance of surface properties as a redox site are discussed.
Studies were conducted to quantitate the evolution of nitrogen oxides (NO(x)) from soybean [Glycine max (L.) Merr.] leaves during in vivo nitrate reductase...Full Text Available
Potato tuber mitochondria oxidizing malate respond to NAD+ addition with increased oxidation rates, whereas mung bean hypocotyl mitochondria do not. This is traced to a low endogenous content...Full Text Available
The potential for oxidation of ammonia in anoxic marine sediments exists through anaerobic oxidation by Nitrosomonas-like organisms, utilizing nitrogen dioxide, coupling of nitrification,...Full Text Available
Pitting behavior of alloy 800 was investigated as a function of temperature and prefilming in high-temperature water. The behavior was characterized in terms of pitting potential (U{sub p}) and pit density (n{sub p}). U{sub p} decreased with increasing temperature and chloride activity. Prefilming of test coupons over a period between 100 h and 5,000 h in ammoniated water at 300 C had no apparent influence on U{sub p} at room temperature, 180 C, and 300 C. However, the number of pits in prefilmed coupons was much higher than in coupons covered with an air passive layer. The effect of prefilming on pit nucleation was investigated in detail with regard to a model and test methods developed by Bianchi, et al. Density of pits in prefilmed coupons was at least 1 order of magnitude higher than in air passive coupons. Maximum pit density was measured after a prefilming period of 100 h. The effect was discussed in terms of Bianchi`s model and in terms ...
The pitting behavior of Alloy 800 was investigated as a function of temperature and prefilming in high temperature water. The pitting behavior was characterized in terms of the pitting potential and the pit density. The pitting potential decreases with increasing temperature and chloride activity. Prefilming of test coupons over a time period between 100 and 5,000 hours in ammoniated water at 300 C has no apparent influence on the pitting potential at room temperature, 180 C and 300 C. However, the number of pits in prefilmed coupons is much higher than in coupons covered with an air passive layer. The effect of prefilming on pit nucleation was investigated in more detail with regard to a model and test methods developed by Bianchi and co-workers. Density of pits in prefilmed coupons is at least one order of magnitude higher than in air passive coupons. Maximum pit density was measured after a prefilming period of 1 00 hours. The effect is discussed in terms of ...
In the VEGA program on radionuclide release from irradiated fuel under severe accident conditions, 10 tests in total were performed at JAEA from 1999 to 2004 under inert and steam atmospheres including the highest pressure or temperature conditions. These tests showed the increase in release rate above 2,800 K or at the fuel liquefaction and the decrease in release rate under elevated pressure, which was a first observation in the world. The data on low-volatility radionuclide release, release from MOX fuel, effect of fuel oxidation, and eutectic reaction with cladding on release were obtained from the tests. The mechanism of pressure effect on release was examined and a new release model with pressure effect was proposed. In addition, the pressure effect on source term evaluation and effectiveness of accident management measures were investigated. This article summarizes the major outcomes described above that have already been published and ...
The diffusion of ion beam injected self-interstitials (I) and their interaction with impurities in crystalline Si has been investigated and modeled. In particular, the I-substitutional carbon (C) interactions have been studied, using a molecular-beam-epitaxy grown Si{sub 1-y}C{sub y} layer interposed between the shallow I-source and a deeper B-spike (marker for I-concentration). Substitutional C atoms are shown to trap I's, to be removed from their substitutional sites, and to form stable precipitates into the C-rich region. The I-trapping mechanism was quantitatively studied by a simulation code. The reactions causing trapping and deactivation are described. In addition, the boron markers approach was extended to the two dimensional (2D) diffusion. High resolution scanning capacitance microscopy was used for quantitative measurements of the 2D boron transient enhanced diffusion induced on a boron delta array by the I's ion beam injected through a ...
The diffusion of ion beam injected self-interstitials (I) and their interaction with impurities in crystalline Si has been investigated and modeled. In particular, the I-substitutional carbon (C) interactions have been studied, using a molecular-beam-epitaxy grown Si_1_-_yC_y layer interposed between the shallow I-source and a deeper B-spike (marker for I-concentration). Substitutional C atoms are shown to trap I's, to be removed from their substitutional sites, and to form stable precipitates into the C-rich region. The I-trapping mechanism was quantitatively studied by a simulation code. The reactions causing trapping and deactivation are described. In addition, the boron markers approach was extended to the two dimensional (2D) diffusion. High resolution scanning capacitance microscopy was used for quantitative measurements of the 2D boron transient enhanced diffusion induced on a boron delta array by the I's ion beam injected through a sub-micron dimension ...
The progress made during the first two years of a program to study the migration of grain boundaries in ceramic oxides is reported. The principal results of the program are concerned with the structure of grain boundaries in ..cap alpha..-Al/sub 2/O/sub 3/, although important new information has also been obtained on grain boundaries in spinels and both germanlum and silicon. Attention is focused on the basal twin boundary in ..cap alpha..-Al/sub 2/O/sub 3/ which had been identified as a model interface in early work. A series of new grain boundaries exemplified by the (11anti23) twin are also discussed briefly as is the rhombohedral twin interface. Earlier results on the first-order (..sigma..=3) twin in spinel have been extended with the development of models for the computer-simulation of high-resolution TEM images of these interfaces. A study of low-angle grain boundaries in spinel is giving new insight into the effect ...
A highly efficient integrated energy conversion system is built based on a methane catalytic decomposition reactor (MCDR) together with a direct carbon fuel cell (DCFC) and an internal reforming solid oxide fuel cell (IRSOFC). In the MCDR, methane is decomposed to pure carbon and hydrogen. Carbon is used as the fuel of DCFC to generate power and produce pure carbon dioxide. The hydrogen and unconverted methane are used as the fuel in the IRSOFC. A gas turbine cycle is also used to produce more power output from the thermal energy generated in the IRSOFC. The output performance and efficiency of both the DCFC and IRSOFC are investigated and compared by development of exact models of them. It is found that this system has a unique loading flexibility due to the good high-loading property of DCFC and the good low loading property of IRSOFC. The effects of temperature, pressure, current densities, and methane conversion on the performance of the ...
We study the emission zone in a single-layer polymer light-emitting diode. The emission zone is found by studying the angular distribution of the electroluminescence. The emission is modeled by accounting for optical interference. We account for birefringence of the anode layer in our model. The active polymer was, however, found to be isotropic. The anode consists of a single-layer of the conducting polymer complex poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (PEDOT-PSS), with enhanced conductivity. As a cathode we use plain aluminum. By using only PEDOT-PSS we avoid having a thin metal layer or indium-tin-oxide as the anode in the path of the escaping light. The active material is a substituted polythiophene with excellent film forming properties. A comparison between the experimental and calculated angular distribution of light emission from a single-layered polymer light-emitting diode was shown to be in ...
This report describes accomplishment of simulations of Pyrochemical Process Operation by using virtual engineering models. The pyrochemical process using molten salt electrorefining would introduce new technologies for new fuels of particle oxide, particle nitride and metallic fuels. This system is a batch treatment system of reprocessing and re-fabrication, which transports products of solid form from a process to next process. As a results, this system needs automated transport system for process operations by robotics. In this study, a simulation code system has been prepared, which provides virtual engineering environment to evaluate the pyrochemical process operation of a batch treatment system using handling robots. And the simulation study has been conducted to evaluate the required system functions, which are the function of handling robots, the interactions between robot and process equipment, and the time schedule of process, in the ...
Recent findings that many human chronic diseases are associated with oxidative stresses have instigated the search for dietary antioxidants. Many phytochemicals, particularly phenolic compounds, have been found to possess strong antioxidant activity and reduce the risks of those diseases. Isoflavones, a special phenolic group found in soybean, have been found to act as antioxidants in some model systems. This study investigated the isoflavone content in a unique nonedible tree fruit, Osage orange [Maclura pomifera (Raf.) Schneid], and methods for the extraction, identification, and quantification of the two major isoflavones, osajin and pomiferin, were developed. The ethyl acetate extract contained 25.7% osajin and 36.2% pomiferin, and the two isoflavones were at 9.5 g kg(-1) of fresh Osage orange. Two model systems, FRAP and beta-CLAMS, were used to measure the antioxidant activity of these two isoflavones. Pomiferin was ...
The structural ordering of oxygen deficient and Co-doped YBCO (YBa_2Cu_3_-_yCo_yO_6_+_x) have been studied experimentally, and by computer simulations of the oxygen ordering in the basal plane of the structure. The calculations are based on the two-dimensional ASYNNNI model and its modifications. Good agreement is established between the ASYNNNI calculations and the experimentally observed structural properties of the double cell ortho-II structure and the oxygen disordering process from Co-doping into the basal plane. A model that relates the superconducting transition temperature T_c(x) of undoped YBCO and T_c(y) of Co-doped YBCO to the formation of specific domains of the two orthorhombic ordered oxygen phases, ortho-I and ortho-II, shows a close agreement with experimental T_c(x) and T_c(y) data of samples prepared under equilibrium conditions. The structural changes as a result of metal ion substitutions and ...
The threshold values of indicator species and ratios delineating the transition between NO_x and VOC sensitivity of ozone formation are assumed to be universal by various investigators. However, our previous studies suggested that threshold values might vary according to the locations and conditions. In this study, threshold values derived from various model simulations at two different locations (the area of Switzerland by UAM Model and San Joaquin Valley of Central California by SAQM Model) are examined using a new approach for defining NO_x and VOC sensitive regimes. Possible definitions for the distinction of NO_x and VOC sensitive ozone production regimes are given. The dependence of the threshold values for indicators and indicator ratios such as NO_y, O_3/NO_z, HCHO/NO_y, and H_2O_2/HNO_3 on the definition of NO_x and VOC sensitivity is discussed. Then the variations of threshold values under low emission conditions ...
The dissolution of NiO cathodes during cell operation is a limiting factor to the successful commercialization of molten carbonate fuel cells (MCFCs). Lithium cobalt oxide coating onto the porous nickel electrode has been adopted to modify the conventional MCFC cathode which is believed to increase the stability of the cathodes in the carbonate melt. The material used for surface modification should possess thermodynamic stability in the molten carbonate and also should be electro catalytically active for MCFC reactions. Two approaches have been adopted to get a stable cathode material. First approach is the use of LiNi{sub 0.8}Co{sub 0.2}O{sub 2}, a commercially available lithium battery cathode material and the second is the use of tape cast electrodes prepared from cobalt coated nickel powders. The morphology and the structure of LiNi{sub 0.8}Co{sub 0.2}O{sub 2} and tape cast Co coated nickel powder electrodes were studied using scanning electron microscopy and ...
The coupling between cerebral metabolic rate of oxygen (CMRO2) and blood flow (CBF) in response to visual stimulation was evaluated by means of a model of oxygen delivery. The model predicted a nonlinear relationship between stimulus-evoked changes of oxygen consumption and blood flow. The magnitude of the CMRO2/CBF ratio index (IO2) was used to indicate the degree of flow-metabolism coupling prevailing in specific areas of the brain during physiological stimulation. Therefore, the index provided a measure of the blood oxygenation level dependent (BOLD) magnetic resonance contrast. To evaluate the changes of IO2 in response to visual stimulation, the model was applied to the effect of a changing flicker rate of a visual stimulus on the magnitudes of CBF, CMRO2, and oxygen diffusion capacity, in the human brain. Positron emission tomography (PET) was used to measure the CBF and the CMRO2 in 12 healthy volunteers who viewed a ...
Apparatus and method for selective measurement of tritium oxide in an environment which may include other radioactive components and gamma radiation, the measurement including the selective separation of tritium oxide from a sample gas through a membrane into a counting gas, the generation of electrical pulses individually representative by rise times of tritium oxide and other radioactivity in the counting gas, separation of the pulses by rise times, and counting of those pulses representative of tritium oxide. The invention further includes the separate measurement of any tritium in the sample gas by oxidizing the tritium to tritium oxide and carrying out a second separation and analysis procedure as described above.
The theoretical principles underlying the formation of oxide and, in particular, anodic oxide coatings on metals produced by chemical oxidation, anodizing in solutions, and anodizing in cold plasmas are reviewed. The mechanisms and conditions of anodic oxidation are described, and the structure of anodic oxide coatings on aluminum, magnesium, beryllium, zinc, cadmium, iron, cobalt, nickel, titanium, zirconium, tantalum, and chromium alloys is examined. Attention is also given to various applictins of anodized coatings. 54 references.
Modern high-resolution electron microscopy (HREM) instruments, which are capable of a point-to-point resolution of better than 0.2 nm, have allowed atomic-scale observations of a variety of internal interfaces. The application of the HREM technique to fcc model systems for the purpose of addressing a number of interface issues will be examined in this paper. Atomic structure observations for heterophase interfaces of metal/metal and metal/metal-oxide systems as well as HREM studies of grain boundaries in NiO and Au will be discussed with emphasis on generic structural features and the role of the interface plane. Comparisons between observed interface structures and atomistic computer modeling results have shown agreements for some interfaces, as well as certain differences in others. A number of structural features are common to both metal and oxide grain boundaries, as well as certain heterophase ...
There is renewed interest in the development of natural gas vehicles in response to the challenge to reduce urban air pollution and consumption of petroleum. The natural gas/diesel dual fuel engine is one way to apply natural gas to the conventional diesel engine. Dual fuel engines operating on natural gas and diesel emit less nitrogen oxides, and less carbon soot to the air compared to conventional diesel engines. The problem is that at light loads, fuel efficiency is reduced and emissions of hydrocarbons and carbon monoxide are increased. This thesis focused on control methods for emissions of hydrocarbons and carbon monoxide in the dual fuel engine at light loads. This was done by developing a reverse flow catalytic converter to complement dual fuel engine exhaust characteristics. Experimental measurements and numerical simulations of reverse flow catalytic converters were conducted. Reverse flow creates a high reactor temperature even when the engine is run at ...
Four advanced oxidation processes (UV/TiO2, UV/IO4^-, UV/S2O8^2^-, and UV/H2O2) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S2O8^2^- (20mM) at pH 8 and 10, and UV/H2O2 (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S2O8^2^- (20mM) and UV/H2O2 (50mM) at pH 8, but three to four times larger for treatment by UV/S2O8^2^- (20mM) at pH 10. ...
The transcriptional silencing of some cell cycle inhibitors and tumor suppressors, such as p16 and retinoic acid receptor beta(2), by DNA hypermethylation at CpG islands is commonly found in human oral squamous carcinoma cells. We examined the effects of the DNA methyltransferase inhibitor 5-Aza-2'-deoxycytidine (5-Aza; 0.25 mg/kg body weight), all-trans retinoic acid (RA; given at 100 microg/kg body weight and 1 mg/kg body weight), and the combination of 5-Aza and the low-dose RA on murine oral cavity carcinogenesis induced by the carcinogen 4-nitroquinoline 1-oxide (4-NQO) in a mouse model. All the drug treatments were done for 15 weeks after a 10-week 4-NQO treatment. Mice in all drug treatment groups showed decreases in the average numbers of neoplastic tongue lesions. The combination of 5-Aza and RA effectively attenuated tongue lesion severity. Although all drug treatments limited the increase in the percentage of proliferating cell ...
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O_2. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation state. ...
The growth of an oxide interfacial layer was recently found to increase the open-circuit voltage (OCV) and efficiency by up to 60 per cent in GaAs metal-semiconductor solar cells. Details of oxidation techniques to provide the necessary oxide thickness and chemical structure and using ozone, water-vapor-saturated oxygen, or oxygen gas discharges are described, as well as apparent crystallographic orientation effects. Preliminary results of the oxide chemistry obtained from X-ray, photoelectron spectroscopy are given. Ratios of arsenic oxide to gallium oxide of unity or less seem to be preferable. Samples with the highest OVC predominantly have As(+3) in the arsenic oxide rather than As(+5). A major difficulty at this time is a reduction in OCV by 100-200 mV when the antireflection coating is vacuum deposited.
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O/sub 2/. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation ...
PurposeCataracts are often considered to be an unavoidable consequence of aging. Oxidative damage is a major cause or consequence of cortical and nuclear cataracts, the most common...Full Text Available
Ethane oxidation was studied in ethane-grown resting cells (mycelia) of an Acremonium sp. and in cell-free preparations of such mycelia. From resting cell experiments evidence was found for a pathway...Full Text Available
Metastable yttrium-oxide films are synthesized using reactive sputter deposition. The yttrium concentration of the as-deposited film is found to vary as a function of the sputter deposition rate. In addition to the synthesis of the cubic equilibrium phase...
Alkali metal doped double perovskites containing manganese and at least one of cobalt, iron and nickel are useful in the oxidative coupling of alkane to higher hydrocarbons.
This patent describes a catalyst composition. It consists of the catalytic oxides of iron, bismuth, molybdenum and magnesium as essential components and optionally the oxides of cobalt, nickel, phosphorus and arsenic.
Background:To determine nutrient requirements by the carbon oxidation techniques, it is necessary to know the fraction of carbon dioxide produced during the oxidative...Full Text Available
Red mud is a waste product of the aluminium refining industry. It is composed of aluminium hydroxide and iron oxide. This study examined the feasibility of using red mud as a catalyst to eliminate volatile organic compounds in atmospheric pollutants. Volatile organic compounds can be eliminated by thermal oxidation between 600 and 1100 degrees C. However, the oxidation of volatile organic compounds can also be accomplished at lower temperatures (200 to 450 degrees C) if a catalyst is present. Currently, the low temperature destruction of volatile organic compounds is not widespread because of the difficulty in deactivating the catalyst. In this study, red mud was calcined in air at 500 degrees C. Under such conditions, the red mud converts to aluminium oxide and iron oxide. These 2 oxides are active and are carbon dioxide selective in the ...
The objective of the study was the kinetic modeling of the effect of storage temperature on the quality and shelf life of chilled fish, modified atmosphere-packed (MAP), and osmotically pretreated with the addition of nisin as antimicrobial agent. Fresh gilthead seabream (Sparus aurata) fillets were osmotically treated with 50% high dextrose equivalent maltodextrin (DE 47) plus 5% NaCl. Water loss, solid gain, salt content, and water activity were monitored throughout treatment and treatment conditions were selected for the shelf life study. Untreated and osmotically pretreated slices with and without nisin (2 x 10(4) IU/100 g osmotic solution), packed in air or modified atmosphere (50% CO(2)-50% air), and stored at controlled isothermal conditions (0, 5, 10, and 15 degrees C) were studied. Quality assessment and modeling were based on growth of several microbial indices, total volatile nitrogen, trimethylamine nitrogen, lipid ...
Smooth and notched specimens of the bearing steel 100Cr6 (SAE 52100) in a bainitic condition were used to determine the S-N curves under tensile, torsional and combined in- and out-of-phase loading. In the area of high-cycle fatigue, crack initiation was most likely caused by inclusions like Titanium Carbonnitrides or Aluminium Oxides. A micro mechanical model for the crack initiation by inclusions was developed. Another model was developed to describe the influence of these inclusions on the lifetime. A weakest-link model, using the statistical distribution of inclusions and surface flaws, was used to describe the endurance limit. (orig.) [German] Es wurden Woehlerlinien unter Zug-Druck-, Torsions- sowie kombinierter phasengleicher und phasenverschobener Zug-Druck- und Torsionsbelastung fuer glatte und gekerbte Proben des Stahls 100Cr6 (SAE 52100) im bainitischen Zustand erstellt. Im Bereich der ...
US Department of Energy (DOE) Order 5820.2A (DOE, 1988) requires performance assessments on all new and existing low-level radioactive waste (LLW) disposal sites. An integral part of performance assessment is estimating the fluxes of radioactive gases such as radon-220 and radon-222. Data needs pointed out by mathematical models drive site characterization. They provide a logical means of performing the required flux estimations. Thorium-230 waste, consisting largely of thorium hydroxide and thorium oxides, has been approved for disposal in shallow trenches and pits at the LLW Radioactive Waste Management Site in Area 5 of the Nevada Test Site. A sophisticated gas transport model, CASCADR8 (Lindstrom et al., 1992b), was used to simulate the transport and fate of radon-222 from its source of origin, nine feet below a closure cap of native soil, through the dry alluvial earth, to its point of release into the atmosphere. ...
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
We report on the fouling of Focused Ion Beam (FIB)-fabricated silicon oxide nanopores after exposure to tap water for two weeks. Pore clogging was monitored by Scanning Electron Microscopy (SEM) on both bare silicon oxide and chemically functionalized nanopores. While fouling occurred on hydrophilic silicon oxide pore walls, the hydrophobic nature of alkane chains prevented clogging on the chemically functionalized pore walls. These results have implications for nanopore sensing platform design.
By means of ESCA the composition and the thickness of passive films formed on austenitic stainless steels were investigated after the attack of nitric acid at various temperatures and acid concentrations. The outermost layers of the oxide film consist of SiO_2, then a layer rich of Cr-oxid follows, containing also some Mo in the four- and sixvalent state. Ni does not contribute to the oxide film. Cr is also enriched in the metal just below the oxide film. (orig.).
The RKR potential energy curves are constructed for the ground states of diatomic hafnium oxide and thorium oxide. Using Lippincott and Hulburt-Hirschfelder potential function the dissociation energies are estimated by curve fitting method. The H-H potential function was found to give a better fit in both cases. The dissociation energies of hafnium oxide and thorium oxide are estimated as 9.04 #+-# 0.02 eV and 10.34 #+-# 0.01 eV respectively. (author).
Targets for heterogeneous transmutation of americium are composed of a support material, the inert matrix and of an americium oxide compound: AmO{sub 2-x} or Am{sub 2}O{sub 3}. In parallel to the studies using americium, simulated compounds of americium oxide, chosen amongst lanthanide oxides, are used. The selection of these compounds is based on theoretical, physical and crystallochemical considerations. In order to assess the influence of impurities composed of lanthanide oxides, resulting from the separation process, on the physical and chemical properties of such a target, synthesis of oxide powders containing impurities associated with the simulated americium oxide, characterizations, crystallographic studies and sodium compatibility tests have been performed. (author)
Titanium oxides were grown anodically to selected final potentials on grade II polycrystalline titanium under different anodization rates. XPS and RBS results show that the oxide consists of primarily TiO2 with a non-stoichiometric oxide/metal interface, with the slower growth rate associated with a thicker layer at the interface. Characterization using TEM reveals that the structure of the oxide evolves from a primarily amorphous phase to islands of crystallites in an amorphous matrix, to an entirely crystalline phase by increasing the polarization potential. Slower growth rates tend to remain crystalline at higher potentials. The mechanical strength of oxide films extracted from load-depth data by nanoindentation varies dramatically for oxide films grown by different rates at 9.4 V, and to a lesser extent at lower potentials. The variation of film strength is ...
Desulphurization of gasoline and kerosene was carried out using organic and inorganic oxidants. Among the organic oxidants used were hydrogen peroxide in combination with acetic acid, formic acid, benzoic acid and butyric acid, while inorganic oxidants used included potassium permanganate and sodium perchlorate. The oxidation of each petroleum oil was carried out in two steps; the first step consisted of oxidation of the feed at moderate temperature and atmospheric pressure while in the second step, the oxidized mixture was extracted with azeotropic mixture of acetonitrile-water. A maximum desulphurization has occurred with NaClO4 and hydrogen peroxide and acetic acid, which are 68% and 61%, respectively in case of gasoline and 66% and 63%, respectively in case of kerosene oil. The FTIR st...
Synergism has been observed during inhibiting initiated oxidation of styrene or tetralin by organic phosphites in the presence of complex compounds of some transition metals. The results are given of non-additive intensification of antioxidative activity of triphenylphosphite (TPP) and tri-(4-methyl-6-tert.-- butyl)-phenyl-phosphite (TMBP) in the process of initiated oxidation of styrene or tetralin with addition of acetylacetonates of cobalt and vanadyl. During styrene oxidation, inhibition of the reaction with chelate complex of vanadyl is weakened considerably when phosphite is added into the reaction system. During tetralin oxidation, postcatalytic (or branched) oxidation is observed only for large concentration of vanadyl complex. Addition of TPP to above complex sharply increases the induction period. When the induction period is completed, oxidation of ...
Our goal was a process to convert methane to higher hydrocarbons oxidatively, since this circumvents thermodynamic yield limits of a strictly degydrogenative process. Keller and Bhasin converted thermodynamic yield limits of a strictly dehydrogenative process. Keller and Bhasin converted methane to higher hydrocarbons by using metal oxides as oxidants, without co-fed oxygen. They stated that selectivity is necessarily poor if gaseous oxygen is present. Jones and Sofranko have also used reducible metal oxides as oxidants in a group of their parents, but later used some of those materials with continuous O{sub 2} feed without much loss of selectivity. Baerns, Lunsford and Otsuka have shown that high selectivity could be possible with co-fed O{sub 2} at least for low O{sub 2} partial pressures, over PbO-A1{sub 2}O{sub 3}, Li-MgO and rare earths. The performance of a group of ...
The oxidative dehydrodimerization of propylene to C/sub 3/-dimers (1,5-hexadiene and benzene) has been examined at 600/sup 0/C and atmospheric pressure using a (Bi/sub 2/O/sub 3/)/sub 0.85/(La/sub 2/O/sub 3/)/sub 0.15/ oxide ion-conducting catalyst in a reactor where a catalyst disk separates a feed of propylene in helium from air. The surface of the disk exposed to propylene was reoxidized not by gaseous O/sub 2/, but by the dissociative adsorption and reduction of dioxygen at the oxidant side of the disk, followed by oxide ion conduction to replace spent lattice oxygen. Selectivity to C/sub 3/-dimers when using lattice oxide migration to reoxidize the catalyst was considerably greater than when O/sub 2/ was added to the propylene feed under the same reaction conditions. This result supports the proposal that lattice oxygen is predominantly involved in the selective ...
Data are presented on the insulating properties and capacitance-voltage (CV) characteristics of metal-oxide-semiconductor (MOS) device-thickness (below approx. 100 nm) native oxides formed by wet thermal oxidation of thin InAlP epilayers lattice matched to GaAs. Low leakage current densities of J=1.4 x 10-9 A/cm2 and J=8.7 x 10-11 A/cm2 are observed at an applied field of 1 MV/cm for MOS capacitors fabricated with 17 nm and 48 nm oxides, respectively. TEM images show that the In-rich interfacial particles which exist in 110 nm oxides are absent in 17 nm oxide films. Quasi-static capacitance-voltage measurements of MOS capacitors fabricated on both n-type and p-type GaAs show that the InAlP oxide-GaAs interface is sufficiently free of traps to support inversion, indicating an unpinned Fermi level. These data suggest that InAlP native ...
This work reports studies of ethanol oxidation on Pt-Sn/C catalysts with nearly the same particle size and identical overall composition having different amounts of oxide and alloyed phases. Results of characterization of physical properties by transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and in situ dispersive X-ray absorption spectroscopy (DXAS) are presented. The variation in the amount of oxide and alloyed phases, promoted by heat treatments in mild temperature conditions, does not produce any significant particle growth. Cyclic voltammetry and oxidation of adsorbed CO in acid medium are used to probe the surface conditions. Data on the electrocatalytic activity towards ethanol oxidation, obtained by potential sweeps and chronoamperometry, are discussed and correlate well with ...
The ODS superalloys MA 6000 and MA 760 were investigated with regard to their behaviour under non-isothermal fatigue stress. For this purpose, strain-controlled thermomechanical and bithermal experiments with different phase relationships between strain and temperature were carried out on the one hand; on the other hand, the deformation behaviour under thermomechanical stress was modelled on the basis of isothermal cyclic creep data. The fatigue experiments show that a diamond-shaped cycle derived from the stress pattern of a turbine blade is clearly less critical than in-phase and out-of-phase cycles. The life of the diamond-shaped cycle is determined by oxidation-induced crack initiation and propagation and can be predicted easily with a suitable damage model. Important damage parameters required by the model can be obtained by the less complicated bithermal fatigue tests. ...
Background: The difficulty of directly measuring cellular dose is a significant obstacle to application of target tissue dosimetry for nanoparticle and microparticle toxicity assessment. As a consequence, the target tissue paradigm for dosimetry and hazard assessment of nanoparticles has largely been ignored in favor of using metrics of exposure (e.g. ?g particle/mL culture medium, particle surface area/mL, particle number/mL). We have developed a computational model of solution particokinetics (sedimentation, diffusion) and dosimetry for non-interacting spherical particles and their agglomerates in monolayer cell culture systems. Particle transport to cells is calculated by simultaneous solution of Stokes Law (sedimentation) and the Stokes-Einstein equation (diffusion). Results: The In vitro Sedimentation, Diffusion and Dosimetry model (ISDD) was tested against measured transport rates or cellular doses for multiple sizes of polystyrene ...
The aim of this paper is to investigate the total ionizing dose (TID) radiation effects on MOS capacitor with nitride/oxide stack gate. The stack gate MOS capacitors are fabricated with 20 nm oxide, 40 nm nitride or 110 nm nitride respectively. Through the analysis of CV curve of the irradiation capacitors, it is found that the degradation of the CV curve is due to a significant increase of interface traps and somewhat smaller oxide charge. It is also shown that the thicker of the nitride, more interface traps and oxide charge will be occurred. (authors)
The procedure of charge-coupled devices (CCD) are investigated by using MOS capacitors for enhancing their ionizing radiation tolerance. Authors have found that the gate oxidation temperature, thickness of SiO_2 gate insulator and high temperature processes after gate oxidation are crucial for determining the radiation tolerance of the devices, and proposed to decrease the thickness of gate insulator, perform gate oxidation at 1000 deg C by means of dry oxidation and minimize the number of high temperature procedure steps after gate oxidation. All stated above is a necessary preparation for priducing radiation hardened charge-coupled devices.
SiSiC is one of selected materials for the thermal chemical hydrogen production IS (Iodine-Sulfur) process at JAERI. SiSiC was tested in boiling sulfuric acid for 1000 hours. The obtained results showed the following facts. The transverse strength was not changed by sulfuric corrosion, high temperature oxidation and oxidation. Silica scale formed on SiSiC by sulfate corrosion and high temperature oxidation had corrosion resistance in boiling sulfuric acid. Bilayer structure of silica scale produced by high temperature oxidation was not affected by sulfate corrosion. (S.Y.).
Cathodic arc deposition is an established and industrially applied technique for the formation of nitrides (e.g. TiN); it can also be used for metal oxide thin film formation. A cathodic arc plasma source with the desired cathode material is operated in an oxygen atmosphere of appropriate pressure, and metal oxides of various stoichiometric composition can be formed on different substrates. We report here on a series of experiments on metal oxide formation by cathodic arc deposition for different applications. Black copper oxide has been deposited on accelerator components to increase the radiative heat transfer between the parts. Various metal oxides such as tungsten oxide, niobium oxide, nickel oxide and vanadium oxide have been deposited on ITO glass to form electrochromic films for window ...
The stoichiometry of photorespiration, S, is defined as the fraction of glycolate carbon photorespired. It is postulated that under steady-state conditions there are two determinants of the ratio of photorespiration to net photosynthesis: the partitioning of ribulose bisphosphate between oxidation and carboxylation, and the partitioning of glycolate between reactions leading to complete oxidation to CO/sub 2/ (S . 100%) and those yielding CO/sub 2/ plus serine (S . 25%). S may be calculated using two independent probes of the system. The physical probe, using an infrared gas analyzer, measured photorespiration and net photosynthesis, and hence their ratio PR/NPS . pn(phys). The metabolic probe employed tracer (3R)-D-(3-/sup 3/H1,3-/sup 14/C)glyceric acid to determine r, the fraction of /sup 3/H retained in the triose phosphates leaving the chloroplasts. It is deduced from the postulated model that S . pn(phys) . r/(1 - r). ...
This multinational, multi-phase spent fuel sabotage test program is quantifying the aerosol particles produced when the products of a high energy density device (HEDD) interact with and explosively particulate test rodlets that contain pellets of either surrogate materials or actual spent fuel. This program has been underway for several years. This program provides data that are relevant to some sabotage scenarios in relation to spent fuel transport and storage casks, and associated risk assessments. The program also provides significant technical and political benefits in international cooperation. We are quantifying the Spent Fuel Ratio (SFR), the ratio of the aerosol particles released from HEDD-impacted actual spent fuel to the aerosol particles produced from surrogate materials, measured under closely matched test conditions, in a contained test chamber. In addition, we are measuring the amounts, nuclide content, size distribution of the released aerosol materials, and enhanced ...
A major factor for the achievement of the desirable performance, efficiency and lifetime of flexible organic electronic devices is the optimization of the encapsulation layers that protect the device active layers by atmospheric gas molecule permeation. The active layers consisted of small molecule and/or polymer organic semiconductors as well as the organic conductors need to be encapsulated into a transparent medium that will provide the necessary protection and maintain their charge generation and transport characteristics. The encapsulation layers are generally consisted of inorganic thin films (silicon oxide-SiO{sub x} and aluminium oxide-AlO{sub x}) deposited onto the polymeric substrates, such as PolyEthylene Terephthalate (PET). In this work, in situ and real-time Spectroscopic Ellipsometry in the ultraviolet spectral region has been implemented in order to investigate the growth of inorganic SiO{sub x} and AlO{sub x} nano-layers onto ...
As part of the studies on coal utilization basics, considerations were given on quantification of sulfur forms of coal and the pyrolysis behavior of sulfur compounds. With the temperature raising oxidation method, a thermo-balance was connected directly to a mass analyzer, and the coal temperature was raised at a rate of 5{degree}C per minute and gasified. Peak division was performed on SO2 and COS production to derive sulfur forms of coal. Using the slow-speed pyrolysis method, production rates of H2S, COS, SO2 and mercaptans were measured at a temperature raising rate of 20{degree}C per minute. Sulfur content in char was also measured. With the quick pyrolysis method, a Curie point pyrolyzer was connected directly to a gas chromatograph, by which secondary reaction is suppressed, and initial pyrolytic behavior can be tracked. All kinds of coals produce a considerable amount of SO2 in the slow-speed pyrolysis, but very little in the quick pyrolysis. Instead, H2S ...
Gas nitridation has shown excellent promise to form dense, electrically conductive and corrosion-resistant Cr-nitride surface layers on Ni-Cr base alloys for use as proton exchange membrane fuel cell (PEMFC) bipolar plates. Due to the high cost of nickel, Fe-base bipolar plate alloys are needed to meet the cost targets for many PEMFC applications. Unfortunately, nitridation of Fe-base stainless steel alloys typically leads to internal Cr-nitride precipitation rather than the desired protective surface nitride layer formation, due to the high permeability of nitrogen in these alloys. This paper reports the finding that it is possible to form a continuous, protective Cr-nitride (CrN and Cr{sub 2}N) surface layer through nitridation of Fe-base stainless steel alloys. The key to form a protective Cr-nitride surface layer was found to be the initial formation of oxide during nitridation, which prevented the internal nitridation typically observed for these alloys, and ...
Gas nitridation has shown excellent promise to form dense, electrically conductive and corrosion-resistant Cr-nitride surface layers on Ni-Cr base alloys for use as proton exchange membrane fuel cell (PEMFC) bipolar plates. Due to the high cost of nickel, Fe-base bipolar plate alloys are needed to meet the cost targets for many PEMFC applications. Unfortunately, nitridation of Fe-base stainless steel alloys typically leads to internal Cr-nitride precipitation rather than the desired protective surface nitride layer formation, due to the high permeability of nitrogen in these alloys. This paper reports the finding that it is possible to form a continuous, protective Cr-nitride (CrN and Cr{sub 2}N) surface layer through nitridation of Fe-base stainless steel alloys. The key to form a protective Cr-nitride surface layer was found to be the initial formation of oxide during nitridation, which prevented the internal nitridation typically observed for these alloys, and ...
Photoelectrochemical oxidation is a potentially interesting method for destroying toxic organic materials. We have studied the photoelectrocatalytic activity of TiO{sub 2} films made by thermal oxidation of titanium, low pressure chemical vapour deposition (LPCVD), and anodisation of titanium. Two model organic compounds have been investigated for photooxidation: methyl phosphonic acid (MPA) which is a nerve gas analogue and 4-chlorophenol (4-CP) which is a chlorinated aromatic compound considered a standard for the evaluation of the TiO{sub 2} / UV processes. In addition to photoelectrochemical characterisation the films have been characterised by profilometry, XRD, AFM, photocurrent spectroscopy and Raman microscopy. Correlations have been made between the physical properties of the thin films and their catalytic activities. The most catalytic sample of thermally oxidised titanium was prepared at 400 deg C, and the ...
In the first part of this paper, IrO_2 electrodes produced by thermal decomposition of H_2IrCl_6 precursor were manufactured using the spin coating deposition technique, where centrifugal forces spread the precursor solution with simultaneous evaporation of the solvent on the rotating Ti substrate. It was found using this technique, that it is possible to obtain thin and uniform IrO_2 coatings with controlled loadings. The influence of the concentration of iridium salt in the precursor solution (c_0) as well as the influence of the rotation speed at which the substrate spins (#omega#) on the IrO_2 loading have been studied using voltammetric charge measurements. From these results, a simple relation has been proposed for the estimation of the IrO_2 loading for a given c_0 and #omega#. In the second part of this paper and from measurements performed using different IrO_2 loadings and formic acid concentrations, the kinetic parameters of the oxidation of formic acid ...
We have studied the dissolution behavior of uraninite, becquerelite, schoepite and uranophane. The information obtained under a variety of experimental conditions has been combined with extensive solid phase characterizations, performed in both leached and unleached samples. The overall objective is to construct a thermodynamic and kinetic model for the long-term oxidation alteration of UO{sub 2}(s), as an analogy of the spent nuclear fuel matrix. We have determined the solubility product for becquerelite (logK{sub s0} 32.7{+-}1.3) and uranophane (logK{sub s0} = 7.8{+-}0.8). In some experiments, the reaction progress has shown initial dissolution of uranophane followed by precipitation of a secondary solid phase, characterized as soddyite. The solubility production for this phase has been determined (logK{sub s0} = 3.0{+-}2.9). We have studied the kinetics of dissolution of uraninite, uranophane and schoepite under ...
Abstract High-mobility group box 1 (HMGB1), a damage-associated molecular pattern (DAMP) molecules, favors tissue regeneration via recruitment and activation of leukocytes and stem cells. Here we demonstrate, in a model of acute sterile muscle injury, that regeneration is accompanied by active reactive oxygen species (ROS) production counterbalanced and overcome by the generation of antioxidant moieties. Mitochondria are initially responsible for ROS formation. However, they undergo rapid disruption with almost complete disappearance. Twenty-four hours after injury, we observed a strong induction of MURF1 and atrogin-1 ubiquitin ligases, key signals in activation of the proteasome system and induction of muscle atrophy. At later time points, ROS generation is maintained by nonmitochondrial sources. The antioxidant response occurs in both regenerating fibers and leukocytes that express high levels of free thiols and antioxidant enzymes, such as superoxide dismutase ...
New studies are always needed to better determine the physico-chemical processes involved in the combustion of natural gas. The understanding of the reaction mechanisms that lead to the formation of nitrogen oxides or volatile organic compounds requires to identify the inner mechanisms which take place during combustion and in particular the mechanisms of formation of intermediate products. The aim of this study is to analyze the thermal degradation of methane and ethane in low pressure pre-mixed stabilized laminar flames condition, because both of these compounds represent the major part of natural gas composition. The main chemical reaction ways identified in the studied flames and responsible for combustion have been identified after a comparison between experimental results and the computerized simulation performed using an a-priori postulated chemical mechanism. This study stresses on the transfer reaction schemes between the different C1, C2 and C3 ...
This work covers three distinct aspects of deformation and fracture during indentations. In particular, we develop an approach to verification of nanoindentation induced film fracture in hard film/soft substrate systems; we examine the ability to perform these experiments in harsh environments; we investigate the methods by which the resulting deformation from indentation can be quantified and correlated to computational simulations, and we examine the onset of plasticity during indentation testing. First, nanoindentation was utilized to induce fracture of brittle thin oxide films on compliant substrates. During the indentation, a load is applied and the penetration depth is continuously measured. A sudden discontinuity, indicative of film fracture, was observed upon the loading portion of the load-depth curve. The mechanical properties of thermally grown oxide films on various substrates were calculated using two different numerical methods. ...
A critical review of the literature revealed no experiments on uranyl ion transfer from an aqueous to a tributyl phosphate phase which positively measured the kinetics of the chemical reaction at the interphase. Drawing isorhythmic lines on a three component diagram gives a complex correlation for the compaction of three sizes of glass beads. Neither the use of thoria sols nor high feed solution concentrations of thorium nitrate gave any significant increase in mean particle diameters over those obtained from nitrate solutions of lower concentrations in flame denitration. A hydraulic film resistance has been detected in the anion exchange of uranyl sulfate into Dowex 2lK, and chloride elution was found to give a higher apparent uranium diffusion coefficient than nitrate elution. The rate of dissolution of mixed thorium-uranium oxides was determined as a function of the per cent of mixed oxides dissolved. Mixing in ...
An updated TRAC 80% large-break loss-of-coolant accident (LBLOCA) has been calculated for the Westinghouse AP600 advanced reactor design, The updated calculation incorporates major code error corrections, model corrections, and plant design changes. The 80% break size was calculated by Westinghouse to be the most severe large-break size for the AP600 design. The LBLOCA transient was calculated to 144 s. Peak cladding temperatures (PCTS) were well below the Appendix K limit of 1,478 K (2,200 F), but very near the cladding oxidation temperature of 1,200 K (1,700 F). Transient event times and PCT for the TRAC calculation were in reasonable agreement with those calculated by Westinghouse using their {und W}COBRA/TRAC code. However, there were significant differences in the detailed phenomena calculated by the two codes, particularly during the blowdown phase. The reasons for these differences are still being investigated. Additional break sizes and ...
FT-IR spectroscopic studies of the adsorption of natural and {sup 18}O-enriched NO gases on thermally and cleaned MgO powders were carried out. The temperature dependence of the IR spectra was investigated to characterize the adsorbate species. Three types [1, 2, and 3] of NO adsorptions were obtained in the wavenumber region of 1500--1000 cm{sup {minus}1}. Those types were examined using density functional theory [(U)B3-LYP/6-31G*] vibrational analyses of (MgO){sub n}-NO cluster calculations. Types 1, 2, and 3 were assigned to monodentate, asymmetric, and symmetric bidentate geometries, respectively. A type 4, a tridentate model which involves a NO{sub 3}-like species, was calculated and was found to give wavenumbers of less than 1,000 cm{sup {minus}1}. The splitting of IR bands of type 3 due to the {sup 15}N{sup 18}O adsorbate was ascribed to the oxygen exchange, {sup 15}N{sup 18}O {yields} {sup 15}N{sup 16}O, via the reaction {sup 16}O-{sup 15}N-{sup 18}O ...
Electricity generation from natural gas in gas turbine units can be made substantially more efficient by preliminary methane conversion to a synthesis gas containing hydrogen and carbon monoxide and/or by the use of some of the synthesis gas produced in industry. An alternative improvement involves the introduction of solid oxide fuel cells (SOFCs) and the use of the synthesis gas in them. In this study, a modified scheme of gas turbine cycle that includes an SOFC, a membrane reactor (instead of a traditional combustion chamber), and a catalytic reactor to perform methane conversion to produce hydrogen (synthesis gas) is proposed. Variations of the energy and exergy efficiencies of the integrated system with operating conditions are provided, showing, for example, that SOFC efficiency is enhanced if the fuel cell active area is augmented. The SOFC stack efficiency can be maximized by reducing the steam generation while increasing the stack size, although such ...
A computational model has been developed to calculate the potential and current distributions in the electrolyte phase and on the electrode surface for a system in which a part of the anode is passivated while the rest remains in the active dissolution state. The computation employs the finite element method allied with a boundary variation and a trial and error technique. From the obtained distributions, the location of the boundary between the active and passive regions on the anode can be predicted. In the case of a crevice, this means that a critical distance into the crevice exists beyond which active corrosion (crevice corrosion) takes place. In addition to the active/passive behavior of the material, solution conductivity, applied potential at the sample's outer surface, crevice gap and depth dimensions, and passive current density influence this critical distance to different degrees. The developed software package may also be used for (i) ...
A type of mesoporous ZrO{sub 2} was synthesized and its phosphate removal potential was investigated in this study. The adsorption isotherm, pH effect, ionic strength effect and desorption were examined in batch experiments. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 29.71 mg P/g. The amount of phosphate adsorbed increased rapidly in the first 5 h and slowly towards the end of the run, suggesting the possible monolayer coverage of phosphate ions on the surface of the adsorbent. The phosphate adsorption tended to increase with a decrease of pH and an increase of ionic strength. A phosphate desorbability of approximately 60% was observed with 0.5 M NaOH, which indicated a relatively strong bonding between the adsorbed PO{sub 4}{sup 3-} and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical ...
New rare earth oxide emitters show greater efficiency than previous emitters. As a result, based on a simple model the efficiency of these emitters was calculated. Results indicate that the emission band of the selective emitter must be at relatively low energy (less than or equal to .52 eV) to obtain maximum efficiency at moderate emitter temperatures (less than or equal to 1500 K). Thus low bandgap energy PV materials are required to obtain an efficient thermophotovoltaic (TPV) system. Of the 4 specific rare earths (Nd, Ho, Er, Yb) studied Ho has the largest efficiency at moderate temperatures (72 percent at 1500 K). A comparison was made between a selective emitter TPV system and a TPV system that uses a thermal emitter plus a band pass filter to make the thermal emitter behave like a selective emitter. Results of the comparison indicate that only for very optimistic filter and thermal emitter properties will the filter TPV system have a ...
Hard surface finishing represents the final manufacturing step for functional areas of machine elements in state-of-the-art production. Raceways of rolling bearing rings are ground and honed to the required low roughness. Plastic deformation is restricted to a narrow edge zone of the hardened steel. Reheating of the machined components below the martensite tempering or bainite transformation temperature results in a marked decrease of the XRD line width on the surface. The investigated samples are made of through-hardened standard bearing steel 100Cr6 (international denotation: SAE 52100). On the basis of a material model that explains the effect as a complex diffusion process of dislocational carbon segregation, i.e. static strain aging, the measured kinetics of the XRD line width reduction is simulated by an Arrhenius-type equation, which describes the rate-controlling reaction step of temper carbide dissolution. The formation of a small white-etching surface ...
Acid Rock Drainage (ARD) is the product formed by the atmospheric oxidation of the relatively common pyrite and pyrrhotite. Waste rock dumps and tailings containing sulfide mineral have been reported at toxic materials producing ARD. Mining in sulphide bearing rock is one of activity which may lead to generation and release of ARD. ARD has had some major detrimental affects on mining areas. The purpose of this study was carried out to develop disposal method for preventing contamination of water and soil environment by waste rocks dump and tailings, which could discharge the acid drainage with high level of metals. Scope of this study was as following: environmental impacts by mine wastes, geochemical characteristics such as metal speciation, acid potential and paste pH of mine wastes, interpretation of occurrence of ARD underneath tailings impoundment, analysis of slope stability of tailings dam etc. The following procedures were used as part of ARD evaluation and ...
This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Nature uses chlorophyll and other porphyrinic pigments to capture and transfer light energy as a preliminary step in photosynthesis. The design of synthetic assemblies of light harvesting and energy directing pigments has been explored through synthesis and characterization of porphyrin oligomers. In this project, pigment electronic and vibrational structures have been explored by electrochemistry and dynamic and static optical measurements. Transient absorption data reveal energy transfer between pigments with lifetimes on the order of 20--200 picoseconds, while Raman data reveal that the basic porphyrin core structure is unperturbed relative to the individual monomer units. These two findings, along with an extensive series of experiments on the oxidized oligomers, reveal that coupling between the pigments is ...
The objectives of the project were (i) to develop a combination iron oxide production and carbon sequestration plant that will use serpentine ores as the source of iron and the extraction tailings as the storage element for CO2 disposal, (ii) the identification of locations within the US where this process may be implemented and (iii) to create a standardized process to characterize the serpentine deposits in terms of carbon disposal capacity and iron and steel production capacity. The first objective was not accomplished. The research failed to identify a technique to accelerate direct aqueous mineral carbonation, the limiting step in the integration of steel production and carbon sequestration. Objective (ii) was accomplished. It was found that the sequestration potential of the ultramafic resource surfaces in the US and Puerto Rico is approximately 4,647 Gt of CO2 or over 500 years of current US production of CO2. Lastly, a computer model ...
Chinese herbs have been and still are widely used as important remedies in Oriental medicine. Over the recent years, a variety of biologically active constituents have been isolated from these sources and confirmed to have multifunctional activity in experimental studies. Honokiol is a small-molecule polyphenol isolated from the genus Magnolia. It is accompanied by other related polyphenols, including magnolol, with which it shares certain biological properties. Recently, honokiol and magnolol have been found to have anti-oxidative, anti-inflammatory, anti-tumor, and anti-microbial properties in preclinical models, without appreciable toxicity. These findings have increased interest in bringing honokiol and magnolol to the clinic as novel therapeutic agents in dermatology. In this review, the findings concerning the major mechanisms of action of honokiol and magnolol are described. Knowledge of the multiple activities of honokiol and magnolol ...
Denting studies have been undertaken in order to assess the influence of the most important parameters which could initiate corrosion of the carbon steel occurring in the tube-tube support plate crevices of some PWR steam generators. Tests have been carried out in model boilers where feedwater was polluted with sea or river water. Specific effects of chloride or sulfate and influence of oxygen content, magnetite addition and pH value were investigated. In magnetite prepacked crevices, denting is obtained within 1000 hrs for seawater pollution of 0.3 ppm chloride at the blowdown. In neutral chloride or in river water, denting is observed only with oxygen addition. Denting prevention is effective in the case of an on-line addition of phosphate, boric acid, or calcium hydroxide. For denting stopping, boric acid or calcium hydroxide is efficient even with a high seawater pollution. Soaks cannot stop denting if they are not followed by an on-line treatment (boric acid, ...
Denting studies have been undertaken in order to assess the influence of the most important parameters which could initiate corrosion of the carbon-steel occurring in the tube-tube support plate crevices of some PWR steam generators. Tests have been carried out in model boilers, feedwater being polluted with sea or river water. Specific effect of chloride or sulfate and influence of oxygen content, magnetite addition and pH value were investigated. In magnetite prepacked crevices, denting is obtained within 1000 hours for sea-water pollution of 0.3 ppm chloride at the blowdown. In neutral chloride or in river water denting is observed only with oxygen addition. Denting prevention is effective in the case of an on-line addition of phosphate, boric acid or calcium hydroxide. For denting stopping, boric acid or calcium hydroxide is efficient even with a high sea-water pollution. Soaks cannot stop denting if they are not followed by an on-line treatment (boric acid, ...
Substantial roles of precipitates such as Zr-Fe-Cr type intermetallic compounds on uniform corrosion and hydrogen pickup of zirconium alloys in pure water autoclave tests were investigated from an electrochemical point of view. In the previous paper, corrosion mechanism was elucidated by the anodic protection-precipitates degradation model. This paper describes the roles on hydrogen pickup. 633 K pure water autoclave test was performed on high purity zirconium, Zr-0.2Fe, Zr-0.2Cr, and Zr-0.1Fe-0.1Cr alloys. Hydrogen analysis after the corrosion test showed that hydrogen pickup ratio of Zr-0.2Fe alloy was about 80%. It was much higher than about 30% of pure Zr and about 10% of both Zr-0.2Cr and Zr-0.1Fe-0.1Cr alloys. Larger hydrogen content was introduced into Zr-0.2Fe alloy than the other ones by the cathodic hydrogen charging under coulombic equivalence. The precipitates at metal-oxide interface could act not only as cathodic sites in the ...
Substantial roles of precipitates such as Zr-Fe-Cr type intermetallic compounds on uniform corrosion and hydrogen pickup of zirconium alloys in pure water autoclave tests were investigated from an electrochemical point of view. In the previous paper, corrosion mechanism was elucidated by the anodic protection-precipitates degradation model. This paper describes the roles on hydrogen pickup. 633 K pure water autoclave test was performed on high purity zirconium, Zr-0.2Fe, Zr-0.2Cr, and Zr-0.1Fe-0.1Cr alloys. Hydrogen analysis after the corrosion test showed that hydrogen pickup ratio of Zr-0.2Fe alloy was about 80%. It was much higher than about 30% of pure Zr and about 10% of both Zr-0.2Cr and Zr-0.1Fe-0.1Cr alloys. Larger hydrogen content was introduced into Zr-0.2Fe alloy than the other ones by the cathodic hydrogen charging under coulombic equivalence. The precipitates at metal-oxide interface could act not only as cathodic sites in the ...
Two major modes of CO adsorption on SiO{sub 2}-supported Pd reflect different extents of back-donation, which is, at least in part, controlled by the local electron density at the adsorption site. The fraction of CO in the bridging mode (B) increases and that of the linear mode (L) decreases, with increasing size of the Pd particles, indicating high electron density at Pd atoms in terraces of close-packed crystal faces, in agreement with Smoluchowski's classical model. For samples reduced at 300{degree}C our data points and those of other authors are located on a common curve of B/L vs metal dispersion. Extensive reduction at 600{degree}C results in significantly lower B/L values, attributed to the incipient formation of a palladium silicide. Oxidation followed by reduction at 300{degree}C destroys the silicide, and the B/L value returns to the original curve.
Two major modes of CO adsorption on SiO{sub 2}-supported Pd reflect different extents of back-donation, which is, at least in part, controlled by the local electron density at the adsorption site. The fraction of CO in the bridging mode (B) increases and that of the linear mode (L) decreases, with increasing size of the Pd particles, indicating high electron density at Pd atoms in terraces of close-packed crystal faces, in agreement with Smoluchowski's classical model. For samples reduced at 300{degree}C our data points and those of other authors are located on a common curve of B/L vs metal dispersion. Extensive reduction at 600{degree}C results in significantly lower B/L values, attributed to the incipient formation of a palladium silicide. Oxidation followed by reduction at 300{degree}C destroys the silicide, and the B/L value returns to the original curve.
This report presented an analysis of incidents gathered by the Canadian upstream oil and gas industry committee in relation to explosive atmospheres in wellbores, vessels, tanks, and piping systems. The aim of the report was to develop industry recommended practices for oil and gas industry fires and explosions. Two accident theory models were used to set out the relationships between hazards, defenses, and losses. Three levels of defenses were identified based on organizational, local workplace, and human factors. An organizational responsibility approach was used to examine the activities of key people with the system. Incidents were analyzed based on an expanded fire triangle used to identify fire and explosion hazards. The study showed that the ignition of hydrocarbons into the air was a factor in nearly 50 per cent of the incidents. A lack of understanding of liquid-hydrocarbon properties was demonstrated in incidents involving oxidized ...
Maternal exposure to ambient air pollution has increasingly been linked to adverse pregnancy outcomes. The evidence linking this exposure to congenital anomalies is still limited and controversial. This case-control study investigated the association between maternal exposure to ambient particulate matter with aerodynamic diameter less than 10 ?m (PM(10)), sulfur dioxide (SO(2)), nitrogen dioxide, nitric oxide (NO), ozone (O(3)), and carbon monoxide (CO) and the occurrence of congenital heart disease in the population of Northeast England (1993-2003). Each case and control was assigned weekly average (weeks 3-8 of pregnancy) of pollutant levels measured by the closest monitor to the mother's residential postcode. Using exposure as both continuous and categorical variables, logistic regression models were constructed to quantify the adjusted odds ratios of exposure to air pollutants and the occurrence of each outcome group. We found exposure to ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl ...
Oestfold Research has trough the project 'Climate accounts for disposal' for Waste Norway developed a model for calculation of net greenhouse gas emissions at the disposal of various waste types. The model is based on life cycle methodology according to the standard IS014044. This model has been used for plastic packaging in the project by adapting the basic values of specific conditions in the municipality of Fredrikstad. Oestfold Research has made an assessment of greenhouse gas emissions for the recycling and material recovery of plastic packaging from households in the district on assignment from Fredrikstad municipality and compared with the current solution where plastic packaging together with residual waste is used for energy utilisation. Based on the population in Fredrikstad and estimated amount of plastic packaging waste arising per household per year the difference in climate impact was ...
We present a proof-of-concept analysis of the measurement of the health damage of ozone (O_3) produced from nitrogen oxides (NO_x=NO+NO_2) emitted by individual large point sources in the eastern United States. We use a regional atmospheric model of the eastern United States, the Comprehensive Air quality Model with Extensions (CAMx), to quantify the variable impact that a fixed quantity of NO_x emitted from individual sources can have on the downwind concentration of surface O_3, depending on temperature and local biogenic hydrocarbon emissions. We also examine the dependence of resulting O_3-related health damages on the size of the exposed population. The investigation is relevant to the increasingly widely used 'cap and trade' approach to NO_x regulation, which presumes that shifts of emission over time and space, holding the total fixed over the course of the summer O_3 season, will have minimal effect on the ...
Cereal straw, a by-product in the production of agricultural crops, is considered as a potentially large source of energy supply with an estimated value of 47 x 10{sup 18} J worldwide. However, there is some debate regarding the actual amounts of straw which could be removed from arable soils without jeopardizing their quality, as well as the potential trade-offs in the overall straw-to-energy chain compared to the use of fossil energy sources. Here, we used a deterministic model of C and N dynamics in soil-crop systems to simulate the effect of straw removal under various sets of soil, climate and crop management conditions in northeastern France. Model results in terms of nitrate leaching, soil C variations, nitrous oxide and ammonia emissions were subsequently inputted into the life-cycle assessment (LCA) of a particular bio-energy chain in which straw was used to generate heat and power in a plant producing bio-ethanol ...
Zirconium and particularly Zr-2.5wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step pro...
In recent years, the influences of acid rain such as the acidification of lake water, on bio-system by the heavy metals from effluent of soils with acid rain and also on the structural materials of buildings are seriously discussed. Sulfur and nitrogen that are contained in fossil fuels are released into the atmosphere by the fuel combustion as their oxides dissolve in rain drops as sulfite and nitrous ions, where they are further oxidized into sulfate and nitrate ions These ions lower the pH of rain water resulting so-called acid rain. Therefore, it is important to accurately determine these ions in rain water for the investigation of reality of acid rain. However, it is not easy to accurately determine these ions, especially for sulfite ions in rain water, since they are quickly oxidized by the catalytic action of metallic ions such as ferric and manganous ions. And light, temperature, pH of solution and also species and ...
The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide ...
The formation of thin SiO_2 layers on silicon and metal silicides was studied by phase- and thickness measurements with Rutherford back-scattering of 2 MeV alfa particles. Thermal oxidation was done in steam and dry oxygen at temperatures between 750 degrees Celsius and 1 100 degrees Celsius, while SiO_2 formation at room temperature was carried out by anodic oxidation. The study of silicon oxidation was done on Si<100>, Si<111> and amorphous silicon substrates. Thermal oxidation of CoSi_2, CrSi_2, NiSi_2, PtSi and TiSi_2 was investigated. The oxidation rates of the silicides were found to be much higher than for silicon. The oxidation process is also diffusion-limited with a higher oxidation rate for steam as compared to dry oxygen. The silicide layers were found to stay intact during thermal oxidation. A ...
Trichloroethene (TCE), a common groundwater contaminant, can be degraded under certain conditions by microorganisms that occur naturally in the subsurface. TCE can be degraded under anaerobic conditions to less chlorinated compounds and ultimately into the non-chlorinated, non-hazardous end product, ethene, via anaerobic reductive dechlorination (ARD). ARD is widely recognized as a TCE degradation mechanism, and occurs in active groundwater remediation and can occur during monitored natural attenuation (MNA). MNA relies on natural processes, such as dispersion and degradation, to reduce contaminant concentrations to acceptable levels without active human intervention other than monitoring. TCE can also be biodegraded under aerobic conditions via cometabolism, in which microbial enzymes produced for other purposes fortuitously also react with TCE. In cometabolism, TCE is oxidized directly to non-hazardous products. Cometabolism as a TCE-degrading process under ...
The morphological development of oxide scales formed on a low Al substituted #beta#-sialon (z=0.2) oxidised for time periods up to 1024h at 1350 C is discussed in relation to oxidation kinetics. The oxidation process is observed to be accompanied by changes in both the phase assemblage of the external layers and their morphology. Thus as the time of oxidation increases beyond 64h the cristobalite-#beta#-yttrium disilicate phase assemblage changes to cristobalite plus #beta#- and #gamma#-yttrium disilicate. In addition to the changes observed for the surface layers, differences are observed in the morphologies of the polished cross-sections. These changes are consistent with an order of magnitude decrease in oxidation rate. (orig.).
Regularities of deformation-induced dissolution of a surface layer of iron oxides in matrixes of iron-based alloys with bcc and fcc lattices have been studied by the methods of M?ssbauer spectroscopy, transmission electron microscopy, and X-ray diffraction. A method of producing iron alloys strengthened by dispersed oxide nanoparticles and alloyed with elements possessing a high affinity to oxygen (titanium and yttrium) has been proposed, which implies a dynamic dissolution of a surface layer of iron oxides upon strong cold deformation and a precipitation of secondary yttrium and titanium nanooxides upon a subsequent high-temperature sintering of mechanically alloyed powders. There has been demonstrated a possibility of oxide strengthening of pure iron upon its interaction with air without...
MCrAlY coatings are widely used on hot section components of gas turbines to provide hot corrosion and/or oxidation protection by formation of an oxide layer on the surface. As the protective oxide scale exfoliates during service, aluminum from the coating diffuses outward for reformation of the protective scale. Aluminum may also diffuse inward due to the differences in composition between the coating and the substrate. Thus, the coatings degrade due to oxidation, oxide scale spallation, and inward and outward diffusion of aluminum. Service life of these coatings is controlled by the aluminum content in the coating, operating temperature and start- shutdown cycles. In-service degradation of CoCrAlY and CoNiCrAlY coatings is presented. A procedure to predict the remaining service life of coatings under oxidizing conditions is discussed. (orig.) 12 refs.
Determination of the specific surface of uranium oxides: UO_2 and U_3O_8 using a simplified equation derived from the Brunauer, Emmett and Teller theory. The method is suitable for samples having a surface between 6 to 50 m"2.
PurposeHeavy metals and other forms of oxidative stress have been implicated as key factors in the formation of age-related cataract in humans. Metallothioneins are...Full Text Available
Altered structure, and hence function, of cellular macromolecules caused by oxidation can contribute to loss of physiological function with age. Here, we tested whether the lifespan of bats, which generally...Full Text Available
The influence of surface oxides of variable composition and nonstoichiometry formed at high temperatures in air on the general corrosion resistance of ferritic chromium steel type 08H17T (Fe-17Cr-1Ti) in weak sulfuric acid has been studied. Anodic passive films formed on steel with different pretreatments have also been examined. The surface oxide of nearly stoichiometric composition formed at 300 C provides for the passive state of steel in sulfuric acid despite its depletion by chromium when compared with that for nonstoichiometric Cr-enriched oxide formed at 600 C. The dissolution and transformation of nonstoichiometric thermal surface oxide in sulfuric acid appear to take place through defect sites, {minus}Fe{sup 2+} ions, and oxygen vacancies of the n-type conductor. The passive film formed on the nonstoichiometric oxide film, which had been produced at 600 C, was found to be ...
BackgroundFree nitric oxide (NO) reacts with sulphydryl residues to form S-nitrosothiols, which act as NO reservoirs. We sought to determine whether thiol-preserving...Full Text Available
The purpose of this study was to synthesize biocompatible polyvinylpyrrolidone (PVP)-coated iron oxide (PVP-IO) nanoparticles and to evaluate their efficacy as a magnetic resonance imaging (MRI)...Full Text Available
A catalytic process for the oxidation of sulfur-containing gases , E.G., sulfur dioxide and simultaneous production of sulfuric acid wherein a sulfur-containing gas is reacted with an oxygencontaining gas in the presence of a catalyst comprising an iron group metal on a solid support comprising a zeolite in a silicaalumina matrix.
4-Hydroxynonenal (HNE), a major electrophilic product of lipid peroxidation, is regarded as both a marker of oxidative stress and a mediator of oxidative damage. At subtoxic concentrations,...Full Text Available
The gelation kinetics of an in situ gelable hydrogel formulated from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) were investigated rheologically. Both Schiff base...Full Text Available
Rheological properties of moderately concentrated solutions of cellulose in methylmorpholine N-oxide-dimethylformamide mixtures containing hydrophilic montmorillonite nanoparticles were studied. Film composite materials were prepared, and their physicomechanical properties and structural organization were studied.
It has been discovered that iron(III) chloride complexes supported on activated charcoal oxidize phosphine under normal conditions. The process accelerates as the concentration of the chloride ions and the proton acid increases.
We report the use of cysteine-substituted mutants in conjunction with in situ oxidation to determine the physical proximity of a pair of engineered cysteines in the pore region of the voltage-gated...Full Text Available
A series of in situ gelable hydrogels were prepared from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) without any extraneous crosslinking agent. The gelation readily...Full Text Available
A multidisciplinary approach was used to study the effects of pollution from a marine fish farm on nitrification rates and on the community structure of ammonia-oxidizing bacteria in the underlying...Full Text Available
This study was conducted to determine by gas chromatography (GC) and mass spectrometry (MS) the identity and the quantity of volatile N products produced during the helium-purged in vivo...Full Text Available
The OH-initiated photo-oxidation of n-butane was used as a source of 1- and 2-butoxy radicals. Reactions producing ketones and other organic compounds are explained. Rates of photolysis were determined and are discussed.
Because copper catalyzes the conversion of H2O2 to hydroxyl radicals in vitro, it has been proposed that oxidative DNA damage may be an important component of copper toxicity....Full Text Available
Oxidative stress has been implicated in the etiology of age-related muscle loss (sarcopenia). However, the underlying mechanisms by which oxidative stress contributes to sarcopenia have not been thoroughly...Full Text Available
The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.
Neurons in the hippocampal CA1 region are particularly sensitive to oxidative stress (OS), whereas those in CA3 are resistant. To uncover mechanisms for selective CA1 vulnerability to OS, we...Full Text Available
The neuronal nitric oxide synthase gene (NOS1) is located at 12q24, a susceptibility region for schizophrenia, and produces nitric oxide (NO). NO has been reported to play important...Full Text Available
Quantitative probing of heterogeneous regions in muscle is feasible with phosphorus-31 magnetic resonance spectroscopy because of the differentiation of metabolic patterns of glycolytic and oxidative...Full Text Available
Thermophilic propionate-oxidizing, proton-reducing bacteria were enriched from the granular methanogenic sludge of a bench-scale upflow anaerobic sludge bed reactor operated at 55°C with a mixture...Full Text Available
Bacterial nitric oxide synthases (bNOS) are present in many Gram-positive species and have been demonstrated to synthesize NO from arginine in vitro and in vivo. However, the physiological role...Full Text Available
BackgroundClara cell protein (CC16), the main secretory product of bronchiolar Clara cells, plays an important protective role in the respiratory tract against oxidative stress and...Full Text Available
The oxidation conditions were investigated for obtaining a higher productivity in the production of high strength carbon fiber from polyacrylonitrile (PAN). The effect of incorporation of 2 % comonomer such as methyl acrylate (MA), acrylate containing carboxylate (SA), acrylamide (AAm), and hydroxyethyl acrylate (HEA) on the oxidation conditions was also investigated. The measurement of DSC and bonded oxygen content revealed that the most effective comonomer for promoting the cyclization of nitril group and the bonding of oxygen was found to be SA, and the second best was AAm. The measurement of tensile strength of carbon fiber showed that the copolymer of SA, HEA, and MA gave a high strength fiber. It took a long time to oxidize the carbon fiber when it was oxidized at a temperature on which double layer structure was not formed. To shorten the production time, a method of combining the upper limit ...
BackgroundTrichloroethylene (TCE) may induce oxidative stress which generates free radicals and alters antioxidants or oxygen-free radical scavenging enzymes.MethodsTwenty...Full Text Available
Systemic administration of lipopolysaccharide (LPS), which causes endotoxemia and systemic inflammation, has been reported to induce expression of the gene for type II inducible nitric oxide synthase...Full Text Available
Three nucleic acid probes, two for autotrophic ammonia-oxidizing bacteria of the beta subdivision of the class Proteobacteria and one for alpha subdivision nitrite-oxidizing bacteria, were developed...Full Text Available
The electrochemical behavior of lanthanide oxides in molten alkaline chloride media is of great concern in pyrochemical processes for advanced nuclear fuel cycle. We have studied the solubilities of various lanthanide oxides in LiCl-KCl eutectic melt. In general, lanthanide oxides appeared to be insoluble/sparingly soluble in LiCl-KCl eutectic at 723 K. However, europium oxide exhibited an abnormal behavior in solubility and redox chemistry. The solubility of europium oxide was measured to be 1-2 order of magnitude higher than those of other lanthanide oxides. This abnormal solubility may be attributable to different electrochemical behavior of europium in the same experimental conditions. Most lanthanides ion exists as trivalent oxidation states. However, we observed divalent europium dissolved in LiCl-KCl molten salt by applying electron ...
1. The effect on rat liver peroxisomal beta-oxidation of feeding diets containing various amounts of dietary oils was investigated. With increasing amounts (5-25%, w/w) of soya-bean oil an apparent,...Full Text Available
This patent describes a method comprising applying a passivation layer of CaF{sub 2} to the surface of a superconductive ceramic oxide by evaporation. The CaF{sub 2} layer is effective to passivate the oxide surface without disrupting the superconductive properties.
Suspensions of denitrifying cells of Pseudomonas perfectomarinus reduced nitrate and nitrate as expected to dinitrogen; but, in the presence of acetylene, nitrous oxide accumulated when nitrate or nitrate...Full Text Available
There is increasing evidence of a biochemical link between lipid oxidation and bone metabolism. Paraoxonase 1 (PON1) prevents the oxidation of low-density lipoprotein (LDL) and metabolizes biologically...Full Text Available
BackgroundArsenic (As) exposure during pregnancy induces oxidative stress and increases the risk of fetal loss and low birth weight.ObjectivesIn...Full Text Available
Anionic peroxidase from tomato (Lycopersicon esculentum) fruit oxidized indoleacetic acid (IAA) slowly in the presence of Mn2+ and dichlorophenol in acetate buffers. The...Full Text Available
The aim of the present study was to evaluate the ameliorative potential of quercetin (QC) against paracetamol (PCM)-induced oxidative stress and biochemical alterations in mice blood. A total of 36...Full Text Available
Evolution of nitrogen oxides (NO(x), primarily as nitric oxide) from soybean (Glycine max [L.] Merr.) leaves during purged in vivo nitrate reductase assays...Full Text Available
Increased oxidative stress with elevated levels of reactive oxygen and nitrogen species (ROS/RNS) plays an important role in the pathophysiology of many disease states. Increased ROS/RNS can...Full Text Available
The goal of this project is to provide materials engineers, chemical engineers and plant operators with a software tool that will enable them to predict localized corrosion of process equipment including fabricated components as well as base alloys. For design and revamp purposes, the software predicts the occurrence of localized corrosion as a function of environment chemistry and assists the user in selecting the optimum alloy for a given environment. For the operation of existing plants, the software enables the users to predict the remaining life of equipment and help in scheduling maintenance activities. This project combined fundamental understanding of mechanisms of corrosion with focused experimental results to predict the corrosion of advanced, base or fabricated, alloys in real-world environments encountered in the chemical industry. At the heart of this approach is the development of models that predict the fundamental parameters that control the ...
This paper reports on hydrolysis of 10 metal salt aqueous solutions of 6 metal oxides that was conducted in supercritical water. Continuous and rapid production of metal oxide fine particles was achieved by mixing a metal salt aqueous solution with preheated water fed from another line. The reaction time required was less than 2 min. Particle size, morphology, and crystal structure of the obtained metal (hydrous) oxides were examined. Particle size (20 to 600 nm) was different among the system but the size range was relatively narrow in all the cases.
Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)
... Title : Effect of Yttrium on the Microstructure of Titanium Alloys,. ... The yttrium was added in the melting stage as an oxide or in the elemental form. ...
Objective of the project is characterization of electrode reactions in molten salt by using metal oxides and silica-based electrode. The scope of project are characterization of metal oxide properties in molten salt and miniaturization of 3-electrode electrochemical test cell. Electrochemical micro-cell for actinide-LiCl-KCl molten salt was newly designed. Electroless and electrochemical deposition technique was applied to Mo coating on quartz tube. From the design of electrode and 3-electrode electrochemical cell suitable for the tests in molten salt electrolyte, so it is anticipated to get the information on the electrochemical behavior of metallic electrode in molten salt and to secure the information on oxidation/reduction behavior of actinide
Measurements were completed on the solubility of cupric and cuprous oxides in liquid water and steam at controlled pH conditions from 25 to 400 C (77 to 752 F). The results of this study have been combined with those reported from this laboratory in two previous EPRI reports to provide a complete description of the solubility of these oxides and the speciation of copper dissolved in liquid water and steam as a function of oxidation state, temperature, pH, and in the case of steam, pressure. These constitute the first set of reliable data for cuprous oxide solubility over this range of conditions. For the more intensively studied CuO case, agreement was found between our results and those of previous studies of its solubility in steam, whereas only partial agreement was evident for its solubility in liquid water. For both oxides this disagreement often amounted to orders of ...
Thermal wet oxidations of GaP and Al{sub 0.4}Ga{sub 0.6}P at 650 degree sign C for various times have been performed. Comparisons are made on oxidation rates and post oxidation morphology. Transmission electron microscopy shows that when oxidizing GaP, polycrystalline monoclinic GaPO{sub 4}{center_dot}2H{sub 2}O forms without noticeable loss of phosphorus. Oxidation for 6 h or more leads to poor morphology resulting in cracks and detachment. A thickness expansion of about 2.5-3 times is noticed as a result of oxidation. In contrast, oxidized Al{sub 0.4}Ga{sub 0.6}P exhibits much better morphology without cracks or detachment from the substrate. The oxide has an almost amorphous-like microstructure. The oxidation process shows typical diffusion-limited reaction at long anneals. Preliminary work on the ...
This articles deals with an approach that has given some key information about the mechanisms of the liquid phase oxidation of butane to acetic acid. This procedure has been developed over the last 34 years; however, much of what will be discussed represents a synthesis of previous insights. Many of the observations are relatively recent and have not been previously published. In principle, this approach should be applicable to many oxidation processes. (orig.)
The behaviour of an elastomeric seal for vehicle brake Tandem master cylinder is measured and analyzed in temperature and brake fluids changed. Working conditions are simulated for different piston rod velocity and cylinder supply pressure, in temperature rising, brakefluid boundary and Nanoaluminum oxide brakefluid oxide brakefluid lubrication. The result shows that Nanoaluminum oxide brakefluid with its ball shape can highly reduce friction coefficient to avoid seal excessive wear and reduce slick slip in brake applications.
The application of kinetic probes that allow one to determine relative reactivities of biologically relevant substrates with oxidizing intermediates in the Fenton reagent (H2O2 plus Fe2+ in acidic aqueous...Full Text Available
A two-step purification protocol was used in an attempt to separate the constitutive NAD(P)H-nitrate reductase [NAD(P)H-NR, pH 6.5; EC 1.6.6.2] activity from the nitric oxide and nitrogen dioxide (NO(x))...Full Text Available
The authors have determined quantitative characteristics for oxide films forming on (111) surfaces of cadmium telluride single crystals on anodic oxidation in 0.1 M KOH: the constants in the Guenterschulze-Betz equation and the film growth constant, which is 2.4 nm/V, from which the activation energy for cadmium telluride electrooxidation has been calculated.
The following methods of quartz ceramics alloying were considered: alloying of initial quartz glass; introduction of alloying additive into water slip of quartz glass; porous materials impregnation with salt aqueous solutions and subsequent salt thermal decomposition with formation of stable oxides in pores of ceramics. Oxygen free compounds BN, SiB_4, SiC, Si_3N_4, REM oxides and transition metal oxides were used as alloying additives. Main properties of the materials and compositions obtained are presented.
During electrolysis of a "2"4"8Cm(III) solution in 2M K_2CO_3 at pH=13, partial oxidation of curium to a higher oxidation state, probably Cm(IV), was observed. The absorption spectra of Cm(III) and Cm(IV) in K_2CO_3 solution were recorded and the molar extinction coefficients of main absorption bands of curium were evaluated. (author).
Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. ...
AQ4N (1,4-bis([2-(dimethylamino-N-oxide)ethyl]amino)5,8-dihydroxy- anthracene-9,10-dione) is a novel alkylaminoanthraquinone N-oxide which, on reduction, forms a stable DNA affinic cytotoxic compound...Full Text Available
Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO{sub 4} volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO{sub 4} species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO{sub 2},xH{sub 2}O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using ...
Metal oxide semiconductor (MOS) integrated circuits, with the benefits of low power consumption, represent the state of the art technology for implantable medical devices. Three significant sources of radiation are classified as having the ability to damage or alter the behavior of implantable electronics; Secondary neutron cosmic radiation, alpha particle radiation from the device packaging and therapeutic doses(up to 70 G{gamma}) of high energy radiation used in radiation oncology. The effects of alpha particle radiation from the packaging may be eliminated by the use of polyimide or silicone rubber die coatings. The relatively low incidence of therapeutic radiation incident on an implantable device and the use of die coating leaves cosmic radiation induced secondary neutron single event upset (SEU) as the main pervasive ionising radiation threat to the reliability of implantable devices. A theoretical model which predicts the susceptibility ...
Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx trap to remove large portion of the sulfur poisons from the ...
In this work the diffusion of ion-beam-injected self-interstitials (Is) and their interaction with impurities in crystalline Si are presented. In particular, the I penetration into a molecular beam epitaxy grown Si structure was studied by means of diffusion effects induced on B spikes, analyzed by a developed simulation code. Trapping effects at sample-surface and bulk are evidenced and modeled. The B marker approach was extended to the two-dimensional (2D) I-diffusion occurring as a consequence of ion implantation through a sub-micron dimension patterned oxide mask. I-source size effects on the I penetration have been found and modeled, quantitatively describing the 2D I-diffusion. The I-substitutional carbon interactions have been also studied, showing the C ability to effectively retain Is. The I-trapping mechanism was quantitatively studied by the simulation code, showing that one I is able to deactivate about two C ...
The adsorption behavior of crystal violet (CV{sup +}) from aqueous solution onto raw (RB) and manganese oxide-modified (MMB) bentonite samples was investigated as a function of parameters such as initial CV{sup +} concentration, contact time and temperature. The Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption models were applied to describe the equilibrium isotherms. The Langmuir monolayer adsorption capacities of RB and MMB were estimated as 0.32 and 1.12 mmol/g, respectively. The mean adsorption energy derived from D-R isotherm for MMB showed that the type of adsorption of dye molecules on this material may be defined as chemical adsorption. The adsorption rate was fast and more than half of the adsorbed-CV{sup +} was removed in the first 55 min for RB and 5 min for MMB at the room temperature. The pseudo-first-order, pseudo-second-order kinetic and the intraparticle diffusion models were used to describe ...
The World Bank is analyzing the role of economic policy instruments for the control of air pollution in Poland, in cooperation with Polish and international experts. The first stage, covering Poland as a whole, was recently completed, jointly financed with the U.S. E.P.A. and the Government of the Netherlands. The second stage, now under way, will extend the analysis into a specific regional framework. Stage 2 is financed by the World Bank, the Polish Government, and the U.K. Environment Know-How Fund. Air Pollution in Poland is overwhelmingly caused by energy production and uses, due to the fact that the Polish economy depends heavily on coal and lignite. At present, vehicles contribute less to total emissions than do coal burning and industrial processes, although they account for 25-35% of nitrogen oxides, carbon monoxide, hydrocarbons and lead; and the concentrated in areas of high population density. The paper shows how economic, technical and meteorological ...
Three independent studies have been conducted for assessing the impact of rocket launches on the earth`s environment. These studies have addressed issues of acid rain in the troposphere, ozone depletion in the stratosphere, toxicity of chemical rocket exhaust products, and the potential impact on global warming from carbon dioxide emissions from rocket launches. Local, regional, and global impact assessments were examined and compared with both natural sources and anthropogenic sources of known atmospheric pollutants with the following conclusions: (1) Neither solid nor liquid rocket launches have a significant impact on the earth`s global environment, and there is no real significant difference between the two. (2) Regional and local atmospheric impacts are more significant than global impacts, but quickly return to normal background conditions within a few hours after launch. And (3) vastly increased space launch activities equivalent to 50 U.S. Space Shuttles or 50 Russian Energia ...
The objectives of this project are to support the DOE direct coal liquefaction process development program and to improve the useful application of analytical chemistry to direct coal liquefaction process development. Independent analyses by well-established methods will be obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, analytical instruments and techniques which are currently underutilized for the purpose of examining coal-derived samples will be evaluated. The data obtained from this study will be used to help guide current process development and to develop an improved data base on coal and coal liquids properties. A sample bank will be established and maintained for use in this project and will be available for use by other researchers. The reactivity of the non-distillable resids toward hydrocracking at liquefaction conditions (i.e., resid reactivity) will be examined. From the literature and data experimentally obtained, ...
A bistable, micromechanical switching device and its buckling stability, heat transfer, and dynamics analyses are summarized. A SEM picture of the device. The buckling element of the microactuator is a U-shaped cantilever ({open_quotes}buckled cantilever{close_quotes} in the picture) consisting of two 0.8 micron-thick polysilicon layers with 0.5 micron-thick oxide insulator sandwiched between them. The 82 micron-long cantilever is buckled by the {open_quotes}tension band{close_quotes} made of 0.5 micron-thick silicon nitride. The snapping action of the microactuator to the down-state (or up-state) is achieved by heating the upper (or lower) polysilicon layer of the buckling cantilever with electric current. Analysis of a snapping action between two buckled states is described. It provides a design framework as well as operation guidelines for the actuator. The buckling stability criterion and the deflection of the buckled cantilever are discussed by using a ...
Carbon capture and storage have been receiving increasing interest lately, mainly as an option to reduce CO{sub 2} emissions from the power sector. The concept could be adapted for production of H{sub 2} as well, which would provide a carbon free energy carrier that could be used for example as transportation fuel. In this doctoral thesis, the option to use chemical-looping technologies to produce H{sub 2} from fossil fuels with CO{sub 2} capture is explored. In chemical-looping combustion, direct contact between fuel and combustion air is avoided. Instead, a solid oxygen carrier performs the task of bringing oxygen from the air to the fuel. Thus, the resulting CO{sub 2} and H{sub 2}O are not diluted with N{sub 2}, and pure CO{sub 2} can easily be recovered by cooling and condensation. The heat of reaction is the same as for ordinary combustion. Chemical-looping reforming uses the same basic principles as chemical-looping combustion, but operates at under stoichiometric conditions. ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two sha...
Coordination of CoCl2 solutions to the silica polyamine composite, WP-1, made with the branched polymer polyethylenimine (PEI) shows irreversible binding resulting from surface oxidation of the Co2+-Co3+. This is not the case for the silica polyamine composite BP-1 made with the linear polymer polyallylamine where reversible binding and no oxidation is observed. These observations suggested that oxidation of the cobalt was related to the greater coordination number available with the branched polyamine relative to the linear polyamine. A study of the kinetics of cobalt binding to WP-1 indicated initial loading of Co2+ at relatively low coordination number followed by desorption of Co2+ leading to oxidation and irreversible binding. Exclusion of oxygen from the composite-cobalt solution mix...
The invention is regeneration and recirculation of nitrogen oxides in the exhaust gas of a nitric acid plant without using any material current and heat energy other than that generated in the process of producing nitric acid. Nitrogen oxide is recovered by at least two adsorbers each containing an acid resistant zeolite molecular sieve and operating in an alternate heat cycle; adsorption occurring at 20-40 degrees C and regeneration at 300-350 degrees C. The hot gas exiting from the oxidation U used in the production of nitric acid is used to regenerate the adsorbers and the nitrogen oxides set free during the said regeneration are introduced into the main feed stream of the nitric acid plant. In the final stage of the regeneration the adsorbers are cooled by rinsing them with exhaust gas or air at a temperature of 20-40 degrees C.
#beta#-sialon ceramics of equal overall compositions but containing amorphous, partly crystalline and almost completely crystalline intergranular phase(s) have been oxidized in oxygen at 1350 deg C for 20 hours. The obtained weight gain curves do not follow the parabolic rate law (#DELTA#W/A_0)"2= k_pt + #beta#. To the extent that crystallization occurs in the oxide scale during the oxidation experiment, the amorphous cross section area through which oxygen most easily diffuses will decrease with time. A brief description of this new rate law is given, and the obtained oxidation curves will be discussed within that framework. 4 refs., 2 tabs., 2 figs.
Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...
One-electron oxidation of several derivatives of pyrazolin-5-one, including the drug antipyrine, were studied by pulse radiolysis of aqueous solutions. All the compounds were found to be oxidized by Br2 rapidly but considerably more slowly by weaker oxidants, such as peroxyl radicals. From redox equilibria using p-methoxyphenol and N,N,N',N'-tetramethyl-p-phenylenediamine as reference compounds, the one-electron oxidation potentials of the methyl-substituted 2-pyrazolin-5-ones were found to be in the range of 0.32-0.39 V versus normal hydrogen electrode. The relevance of these findings to the properties of the drug nafazatrom is discussed. Antipyrine was found to have a much higher oxidation potential, estimated as 1.2-1.5 V, which is rationalized on the basis of the phenyl substitution and lack of resonance stabilization of the radical cation.
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern ...
Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a ...
A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe{sub 2}O{sub 3} powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe{sub 2}O{sub 3} powder was used to oxidize a high carbon coal char in an inert gas removing 88% of ...
Slurry aluminizing is one method of protecting titanium alloys and intermetallics at temperatures at which oxidation would otherwise significantly degrade mechanical properties. The technique produces a continuous layer of alumina-forming TiAl_3 on exposed surfaces. The influence of composition, film thickness, and diffusion temperature upon the oxidation resistance of these slurry aluminides was studied in cyclic tests to 816degC (1500deg F). Degradation of slurry aluminized #beta#-titanium alloy and #alpha#-Z titanium aluminide intermetallic occurs by localized oxidation at cracks in the coating layer. These cracks are probably due to mismatch of coefficients of thermal expansion between the coatings and substrates. Addition of silicon to the slurry modifies the oxidation behaviour around a crack by introducing a continuous layer of titanium silicide at the boundary of the aluminide coating and ...
The generation of acidic mine drainage is based on the oxidation dissolution of sulfide minerals due to the contact of ores with the natural water and the air. Namely, the sulfuric acid promotes the dissolution of sulfide minerals and gangue minerals, and Fe{sup 2+} is further oxidized to turn into Fe{sup 3+}, which acts as an oxidizer for other sulfide minerals and promotes the dissolution of the same. This paper roughly describes a mine drainage treatment focusing on an Fe{sup 2+} neutralization method and an iron bacteria oxidation method. The iron bacteria oxidation method is a method of oxidizing Fe{sup 2+} into Fe{sup 3+} by using iron bacteria, and then removing Fe{sup 3+} with calcium carbonate. This method has been used for treating the drainage in the Sakuhara Mine and the former Matsuo Mine, with good results. The paper finally introduces, as ...
Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions - with and without in situ wet oxidation - were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 deg. C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and ...
A duplex surface treatment technique based on calorizing and plasma nitriding was developed to improve the wear and oxidation resistance of H13 steel at high temperatures. The effects of the relative thickness of the calorized layer to the depth of plasma nitriding on the wear and oxidation properties at temperatures up to 900 C were investigated in this work. High-temperature wear tests were performed at 500 C with dry conditions in open air using a ball-on-disk type tribotest machine. Isothermal oxidation tests were performed at 900 C for up to 100 h under controlled atmosphere. The results indicated that the specimens with a calorized layer as an intermediate phase between the surface duplex layer and the base metal showed higher wear and oxidation resistance than the specimens with a nitrided layer alone. During exposure to elevated temperatures, the aluminum in the calorized layer diffused to the ...
Papers are presented on the development of oxidation- and sulfidation-resistant ferritic alloys; the microstructural stability of sulfidation-resistant FeCrAl stainless steels around 500 C; age hardening in Fe-Mn-Al-C austenitic alloys; the oxidation/corrosion behavior of low-Cr Fe-Cr-Ni alloys containing Zr or Nb; the high temperature oxidation/corrosion of iron-based superalloys; and the role of Mo in the Na/sub 2/SO/sub 4/ induced corrosion of superalloys at high temperature. Topics discussed include the effect of variations of Co content on the cyclic oxidation resistance of selected Ni-base superalloys; high temperature oxidation of Fe based alloys; the morphological development of high temperature oxide scales of Fe-Mn-Al base alloys; and the oxidation of an Fe-Mn-Al-C alloy at 1000 C. Consideration is given to the corrosion properties ...
Observational evidence is presented for the nucleation of condensation nuclei (CN) in the clear air adjacent to an isolated, marine, cumulus cloud. Two separate regions of particle nucleation are identified: one located above the cloud top, and the second located downwind of the cloud near the level of the anvil outflow. The regions of high CN concentrations were located in extremely clean marine air, with unactivated aerosol surface area (excluding the nucleation mode) less than 2 sq micrometers/cu cm, air temperature -31 C, and higher relative humidities than the undisturbed environment. Vertical profile measurements downwind of the cloud showed that CN concentrations at the level of the anvil outflow (4.9 km) were 8 times greater than at any other level between the surface and 5.3 km. A conceptual model is formulated in which aerosol particles, sulfur dioxide (SO2), sulfuric acid vapor (H2SO4), dimethyl sulfide (DMS), and ozone (O3) from the boundary layer are ...
Purpose: An animal model is used to investigate whether MR angiography combined with super-paramagnetic particles of iron oxide (SPIO) is suitable for detecting thromboses. Methods: 42 rats in groups of 7 each were examined on days 1, 3, 5, 7, 9 and 11, respectively, after mechanical/chemical thrombus induction in a 1.5 Tesla magnet with a FISP sequence (TR/TE/FA 50 ms/6 ms/40 ). Imaging was performed before and up to 90 minutes after intravenous injection of 30 {mu}mol FE/kg BW of the experimental SPIO (hydrodynamic diameter, 34{+-}17 nm LLS; R1 and R2 relaxivity at 0.47 T, 31 and 57 L/(mmol*s)). MIP reconstructions of MR angiographies were submitted to consensus assessment by two examiners using histology as the gold standard. Results: The image quality of MIP reconstructions was rated as good in 38 of 42 cases. With regard to thrombotic vessel occlusion, MR angiography coincided with histology in 17 of 42 cases and differed in 25, lumen ...
In this study, a regional dynamical model (WRF) is used to drive biogenic emission models to calculate high resolution (10 x 10 km) biogenic emissions of isoprene (C_5H_8), monoterpenes (C_1H_1_6), and nitric oxide (NO) in China. This high resolution biogenic inventory will be available for the community to study the effect of biogenic emissions on photochemical oxidants in China. The biogenic emissions are compared to anthropogenic emissions to gain insight on the potential impact of the biogenic emissions on tropospheric chemistry, especially ozone production in this region. The results show that the biogenic emissions in China exhibit strongly diurnal, seasonal, and spatial variations. The isoprenoid (including both isoprene and monoterpenes) emissions are closely correlated to tree density and strongly vary with season and local time. During winter (January), the biogenic isoprenoid emissions are ...
From the alkalised crude extract of Symphytum cordatum (L.) W.K. roots, pyrrolizidine alkaloids (PAs) were extracted as free tertiary bases and polar N-oxides in a merely one-step liquid-liquid partitioning (LLP) in separation funnel and subsequently pre-fractionated by preparative multiple-development (MD) thin-layer chromatography (TLC) on silica gel plates. In this way three alkaloid fractions of different polarities and retention on silica gel plates were obtained as: the most polar N-oxides of the highest retention, the tertiary bases of medium retention, and diesterified N-oxides of the lowest retention. The former fraction was reduced into free bases by sodium hydrosulfite and purified by LLP on Extrelut-NT3 cartridge. It was further analysed together with the two other fractions by high-performance liquid chromatography (HPLC)-ion-trap mass spectrometry with atmospheric pressure chemical ionization (APCI) interface ...
The Cox proportional hazards model is the most widely used model for survival analysis because of its simplicity. The fundamental assumption in this model is the proportionality of the hazard function....Full Text Available
The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically active and selective and showed no formation of oxygenates. In the present study the ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO{sub 2}, PrO{sub 2}), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes: small cubic (oxide) and large plate-like (tetragonal) structures. The ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes: small cubic (oxide) and large plate-like (tetragonal) structures. The conversion ...
Basic studies of the oxidation resistance of Fe-Cr binary and Fe-Cr-Ni ternary alloys in pure oxygen have shown that the excellent corrosion resistance of Alloy 800 is explicable in terms of the low defect concentrations and diffusion rates in the oxide forming on alloys of this composition in sufficiently oxidising environments. The performance of Alloy 800 in environments of particular importance to nuclear power generation is briefly reviewed to determine to what extent ideas derived from the basic studies of Fe-Cr-Ni ternary alloys are borne out in practice. The good corrosion resistance of Alloy 800 in steam and CO_2 and, to some extent, in molten salt environments is in agreement with the behaviour of ternary alloys in oxygen. Minor aliovalent alloying additions are only expected to have a significant effect on the oxidation resistance of Alloy 800 if they favour the formation of breakthrough duplex ...
The aim of this work is to test the catalytic oxidation of pyridine over zeolite-supported catalysts and to compare the difference in their activities for the oxidation of pyridine. The catalytic oxidation of pyridine pollutant on a series of copper-supported catalysts, inclusive of Cu/beta, Cu/ZSM-5, Cu/MCM-41 and Cu/{gamma}-Al{sub 2}O{sub 3}, in the presence of excess oxygen was studied. The activity of the copper-supported catalysts for the pyridine oxidation could be correlated with the binding energy of oxygen coordinated to metal copper, while the ability to control the yield of NO{sub x} appeared to be strongly dependent on the binding energy of NO bonded to metal copper. On these catalysts, two copper species, Cu(H{sub 2}O){sub 6}{sup 2+} ions and CuO were identified, in which Cu{sup 2+} ions had higher activity for the NO{sub x} control but poorer activity for the pyridine ...
Dominating factors in plasma nitriding and plasma condition that makes nitriding possible in plasma nitriding process of metals having hard oxide film were studied. In case of stainless steel, oxide film sputtering was easier comparing to nitriding layer. Three phenomena such as sputtering of oxide layer, formation of nitriding layer and sputtering of nitriding layer occurred simultaneously. Nitriding was achieved when the formation of nitriding layer reached the peak comparing to the removal of nitriding layer after the removal of oxide layer. Situations of metallic surface of stainless steel in surface nitriding were divided into four categories and they were, situation where oxide layer remained as it is, situation where nitriding layer was formed although oxide layer remained in some part, situation where only nitriding layer was formed and situation where ...
Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on ...
A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization (FGD) system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and -0.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. ...
Boron is implanted in crystalline silicon through oxide layers with different thicknesses. The implantation is carried out at various doses and energies of interest in ultra large scale integration (ULSI) application. Rapid thermal annealings (RTA) are used to obtain shallow junctions and electrical activation of the B atoms. However, transient enhanced diffusion induced by implantation damage can be observed. The boron concentration profiles before and after annealing are obtained with secondary ion mass spectrometry (SIMS). It is found that the diffusion transient in the tail region of the boron profile increases with decreasing oxide thickness. Even more, if the implantation damage concerns mostly the oxide, i.e. when the concentration peak is located in this oxide, the oxygen knocked into the silicon substrate could play this way an important role in restricting the boron diffusion, which is good to ...
Boron is implanted in crystalline silicon through oxide layers with different thicknesses. The implantation is carried out at various doses and energies of interest in ultra large scale integration (ULSI) application. Rapid thermal annealings (RTA) are used to obtain shallow junctions and electrical activation of the B atoms. However, transient enhanced diffusion induced by implantation damage can be observed. The boron concentration profiles before and after annealing are obtained with secondary ion mass spectrometry (SIMS). It is found that the diffusion transient in the tail region of the boron profile increases with decreasing oxide thickness. Even more, if the implantation damage concerns mostly the oxide, i.e. when the concentration peak is located in this oxide, the oxygen knocked into the silicon substrate could play this way an important role in restricting the boron diffusion, which is good to ...
In this work we present an ultra-low temperature method for the oxidation of an amorphous silicon-carbide-nitride (SiCN) material. The SiCN is deposited on silicon substrates by plasma enhanced chemical vapor deposition using CH{sub 4}, SiH{sub 4}, and N{sub 2} chemistry. The physical and chemical properties are characterized for the as-deposited SiCN and post-oxidized films are discussed. The SiCN film is exposed to oxygen plasma, where it undergoes a chemical transformation into a binary SiO{sub 2} material system. A 1.7 nm/min oxidation rate is typical for this process and compares favorably to oxidation methods utilizing much higher temperatures. The substrate temperature remains extremely low throughout the oxidation process, T{sub s} < 200 deg. C. Changes in film stress, optical constants, film thickness, surface roughness, and film density are measured. Chemical ...
'The interactions of carbon tetrachloride with strongly basic oxides and hydroxides have been studied by several techniques in order to understand the surface reactions and the subsequent bulk reactions that result in the destruction of the chlorinated hydrocarbon. Emphasis has been placed on understanding the surface phases, as well as the bulk phases, that are present during these transformations. As a result of the study with barium oxide, a reaction cycle has been demonstrated that may have practical significance in the removal of chlorinated hydrocarbons.'
In most industrial processes operating at elevated temperatures, protective oxide layers perform a vital duty in protecting the underlying metallic alloys from process gases. Coal-fired combined cycle power generation systems present a number of process conditions in which the properties of the protective oxide layers are particularly important. This paper discusses two of these particular conditions: (1) `erosion/corrosion` of in-bed heat exchanger tubing and (2) thermal cycling of hot gas path components. For both these situations, the desirable properties of protective scales are outlined. The behaviour of scales in practice are highlighted. 33 refs., 6 figs., 2 tabs.
Chlorophyll a, chlorophyll b, and bacteriochlorophyll a in aqueous micellar solutions of Trition X 100 (2%) are readily oxidized by pulse-radiolytically generated N_3., Br_2"-., and (SCN)_2"-. radicals at nearly diffusion-controlled rates. The kinetic study suggests that pigment molecules occupy multiple sites in the micelle. Pheophytin a is only oxidized by N_3. and Br_2"-. radicals. The absolute spectra and the molar extinction coefficients of chlorophyll a, bacteriochlorophyll a, chlorophyll b, and pheophytin a cations have been determined. The chlorophyll a cation has been observed in the presence of pigment aggregates.
Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)
A nitrogen oxides decreasing combustion method comprising: mixing a fuel and air with each other; bringing the mixture obtained into contact with a packed catalyst; and adding a fresh supply of the fuel to the stream obtained to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion, characterized in that only a catalytic reaction or combustion occurs at the packed catalyst; the temperature of the packed catalyst is kept lower than the ignition temperature of the mixture; the adiabatic flame temperature which is reached by the non-catalytic thermal combustion of the mixed gas is lower than the temperature at which the nitrogen oxides occur. 39 figs.
This patent describes a nitrogen oxides decreasing combustion method which comprises: a first step of mixing a fuel and air with each other; a second step of bringing the mixture obtained in the first step into contact with a packed catalyst such that only catalytic combustion occurs; and a third step of adding a fresh supply of the fuel to a stream obtained from the second step to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion. The temperature of the packed catalyst is lower than the ignition temperature of the mixture and the adiabatic flame temperature of the mixed gas is lower than a temperature at which the nitrogen oxides occur.
Cr_2O_3 scales are found to form on Alloy 800 and a similar pure ternary alloy in air, and 1 and 50 atm. helium containing oxidizing impurities typical of those in an SGHTR. The strong temperature dependence and neglibible helium overpressure dependence indicate that gas transport through the scales is not rate controlling. Surface oxidation rates are therefore controlled by solid state diffusion and the low oxygen partial pressure dependence of the oxidation rate in Alloy 800 is ascribed to the presence of extrinsic defects in the Cr_3O_3 (due to doping by alloying elements) or to the presence of short circuit diffusion paths. (Auth.).
We report on the single-particle properties of lanthanide-ion doped oxide nanoparticles. We have demonstrated that their size can be accurately determined from their luminosity. The optically determined size distribution is in very good agreement with the distribution obtained from transmission electron microscopy (TEM). We also showed that the photobleaching of these nanoparticles is related to a reduction process and that we can use it to sense in a concentration-dependent manner the presence of an oxidant like H2O2. Finally, we propose a way to perform nanoparticle-protein coupling and to determine the protein-nanoparticle ratio at the single-particle level.
This work deals with kinetic description of carbothermic reduction of iron oxides using microwaves as power source. Previous researches show that it is possible to conduct this kind of process successfully, but real kinetic comparisons between conventional and microwaves procedure have been presented partially. The aim of this work is to describe reduction kinetics, taking into account how the iron oxide is reduced by microwaves compared with conventional energy supply. In this study the authors used iron ore in pellet shape and dust. They found that both, pellet and dust reduction stops when it reaches approximately 40%, even at whole power.
Lanthanide-ion doped oxide nanoparticles were functionalized for use as fluorescent biological labels. These nanoparticles are synthesized directly in water which facilitates their functionalization, and are very photostable without emission intermittency. Nanoparticles functionalized with guanidinium groups act as artificial toxins and specifically target sodium channels. They are individually detectable in cardiac myocytes, revealing a heterogeneous distribution of sodium channels. Functionalized oxide nanoparticles appear as a novel tool particularly well adapted to long-term single-molecule tracking.
Separation of lithium isotopes was investigated by chemical ion exchange with a hydrous manganese(IV) oxide ion exchanger using an elution chromatography. The capacity of manganese(IV) oxide ion exchanger was 0.5 meq/g. The heavier lithium isotope was enriched in the solution phase, while the lighter isotope was enriched in the ion exchanger phase. The separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factor of {sup 6}Li{sup +} -{sup 7}Li{sup +} isotope pair fractionation was 1.018.
Uranium has varying degrees of oxidation (+4 and +6) and is responsive to changes in the redox potential of the environment. It is deposited at the reduction barrier with the participation of biota and at the sorption barrier under oxidative conditions. Iron (hydr)oxides are the strongest sorbents of uranium. Uranium, being an element of medium biological absorption, can accumulate (relative to thorium) in the humus horizons of some soils. The high content of uranium in uncontaminated soils is most frequently inherited from the parent rocks in the regions of positive U anomalies: in the soils developed on oil shales and in the marginal zone of bogs at the reduction barrier. The development of nuclear and coal-fired power engineering resulted in the environmental contamination with uranium....
One of the main problems related to optical thin film materials used in high power laser environments is the catastrophic damage caused to them due to laser irradiation. While the influence of ion bombardment on the optical properties of oxide thin films is now a well understood subject, the morphology and crystalline behaviour of these films under ion incidence is not so well studied. Hence, it is of great importance to investigate the effects of ion bombardment during growth on the microstructure and crystalline behaviour of oxide materials.
We present a new approach for growing Si nanowires directly from a silicon substrate, without the use of a metal catalyst, silicon vapor or CVD gasses. The growth can be performed in a furnace type configuration at moderate temperatures or in localized regions by resistive heating. Since the silicon wires grow directly from the silicon substrate, they do not need to be manipulated nor aligned for subsequent applications. Wires in the 20-50 nm diameter range with lengths over 80 ?m can be grown by this technique. We have studied the effects of various growth parameters, including temperature, substrate orientation, initial sample cleaning and carrier gasses. Results indicate that most important parameters in the growth of the nanowires are the surface cleaning, the temperature and the type of carrier gas used. A model is proposed, which involves an oxide catalyst for the process, with the growth of the nanowires enabled by a significantly ...
The purpose of the Microelectronic Evaluation Laboratory at Sandia is to develop a program for evaluating CMOS LSI (complementary metal oxide silicon - large scale integrated) technology devices which are being used for the first time in a weapon system. These evaluations are based on accelerated aging studies and electrical tests to determine the reliability and life of the devices. In accelerated aging, specific, controlled stresses are applied to the device to accelerate time-to-failure. Data are used tin mathematical models to estimate life in acutal use. The stresses used for this technology are temperature and voltage. The devices are stored at temperatures with or without voltage applied (steady-state or cyclical) and periodically tested until at least 50% failures are encountered. Since most current technologies use epoxy-die-attachment, aging temperatures must be under 200/sup 0/C. This delays device failure, and a 16% failure level is ...
A brief review and assessment of field measurement programs that provide data for mixed layer diffusion research is presented. The majority of programs emphasize either the meteorological aspects of the mixed layer or plume characterization. Few programs are available that provide the complimentary blend of plume and appropriate meteorological measurements needed to adequately validate mixed layer diffusion theory. Three major U.S. EPA (Environmental Protection Agency) field programs that provide data bases for model development and validation of mixed layer diffusion processes are described and discussed in more detail. The Regional Air Pollution Study (RAPS) focused on measurements of surface and mixed layer turbulent transport processes in the urban environment. The Tennessee Plume Study (TPS) obtained a database with coincident measurement of boundary layer turbulent structure and plume dispersion for a large coal-fired power plant in nonuniform terrain over ...
One of the limiting contributors to the heat load constraint for a long term spent fuel repository is the decay of americium-241. A possible option to reduce the heat load produced by Am-241 is to eliminate it via transmutation in a light water reactor thermal neutron environment, in particular, by taking advantage of the large thermal fission cross section of Am-242 and Am-242m. In this study we employ lattice loading optimization techniques to define the loadings and arrangements of fuel pins with blended americium and uranium oxide in boiling water reactor bundles, specifically, by defining the incineration of pre-loaded americium as an objective function to maximize americium transmutation. Subsequently, the viability of these optimized lattices is tested by assembling them into bundles with Am-spiked fuel pins and by loading these bundles into realistic three-dimensional BWR core-wide simulations that model multiple reload cycles and ...
Here we report normal-state conductance measurements of three different types of superconducting tunnel junctions that are being used or proposed for quantum computing applications: p-Al/a-AlO/p-Al, e-Re/e-AlO/p-Al, and e-V/e-MgO/p-V, where p stands for polycrystalline, e for epitaxial, and a for amorphous. All three junctions exhibited significant deviations from the parabolic behavior predicted by the WKB approximation models. In the p-Al/a-AlO/p-Al junction, we observed enhancement of tunneling conductances at voltages matching harmonics of Al-O stretching modes. On the other hand, such Al-O vibration modes were missing in the epitaxial e-Re/e-AlO/p-Al junction. This suggests that absence or existence of the Al-O stretching mode might be related to the crystallinity of the AlO tunnel barrier and the interface between the electrode and the barrier. In the e-V/e-MgO/p-V junction, which is one of the candidate systems for future superconducting qubits, we observed ...
Patients suffering from depression frequently display hyperactivity of the hypothalamic-pituitary-adrenal axis (HPA) resulting in elevated cortisol levels. One main symptom of this condition is anhedonia. There is evidence that exercise training can be used as a rehabilitative intervention in the treatment of depressive disorders. In this scenario, the aim of the present study was to assess the effect of an aerobic exercise training protocol on the depressive-like behavior, anhedonia, induced by repeated dexamethasone administration. The study was carried out on adult male Wistar rats randomly divided into four groups: the "control group" (C), "exercise group" (E), "dexamethasone group" (D) and the "dexamethasone plus exercise group" (DE). The exercise training consisted of swimming (1 h/d, 5 d/wk) for 3 weeks, with an overload of 5% of the rat body weight. Every day rats were injected with either dexamethasone (D/DE) or saline solution (C/E). Proper positive controls, using ...
The study of tropospheric kinetics underlies global change because key greenhouse gases are photochemically active. Modeling of tropospheric chemistry on a global scale is essential because some indirect greenhouse gases are short-lived and interact in a non-linear fashion. It is also extremely challenging, however; the global change grid is extensive in both the physical and temporal domains, and critical lower atmospheric species include the organics and their oxidized derivatives, which are numerous. Several types of optimization may be incorporated into kinetics modules to enhance their ability to simulate the complete lower atmospheric gas phase chemical system. (1) The photochemical integrator can be accelerated by avoiding matrix and iterative solutions and by establishing families. Accuracy and mass conservation are sacrificed in the absence of iteration, but atom balancing is restorable post hoc. (2) Chemistry can be arranged upon the ...
Surface analytical studies of high nitrogen austenitic stainless steels exposed to deaerated 0.1M HCl have revealed that nitrogen alloying additions influence the composition of salt layers and the passive film/alloy interface. In this study the authors employ electrochemical techniques and variable angle X-ray Photoelectron Spectroscopy (XPS) to examine the passive films formed on a series of austenitic stainless steels, Fe18Cr8Ni, Fe18Cr8Ni0.2N, Fe20Cr20Ni, Fe20Cr20Ni6Mo and Fe20Cr20Ni6Mo0.2N, in acidic chloride aqueous solution. In addition, several other model alloys, Fe19Cr, Fe19Cr9Ni, Fe19Cr2.5Mo, and Fe19Cr9Ni2.5Mo, were examined before and after electrochemical surface nitriding, a technique proven to have an effect analogous to N alloying. It was shown that nitrogen, nickel and molybdenum additions independently and in certain combinations stimulate selective dissolution of iron, resulting in a significant enrichment of chromium beneath the passive film. ...
Surface analytical studies of high nitrogen austenitic stainless steels exposed to deaerated 0.1M HCl have revealed that nitrogen alloying additions influence the composition of salt layers and the passive film/alloy interface. In this study the authors employ electrochemical techniques and variable angle X-ray Photoelectron Spectroscopy (XPS) to examine the passive films formed on a series of austenitic stainless steels, Fe18Cr8Ni, Fe18Cr8Ni0.2N, Fe20Cr20Ni, Fe20Cr20Ni6Mo and Fe20Cr20Ni6Mo0.2N, in acidic chloride aqueous solution. In addition, several other model alloys, Fe19Cr, Fe19Cr9Ni, Fe19Cr2.5Mo, and Fe19Cr9Ni2.5Mo, were examined before and after electrochemical surface nitriding, a technique proven to have an effect analogous to N alloying. It was shown that nitrogen, nickel and molybdenum additions independently and in certain combinations stimulate selective dissolution of iron, resulting in a significant enrichment of chromium beneath the passive film. ...
Pale colored BiY_1_-_xR_xGeO_5 (R=rare-earth from Pr to Yb) polycrystalline samples exhibit a crystalline phase isostructural with the orthorhombic Pbca (No. 61) structure-type established for BiYGeO_5 and BiYbGeO_5. R occupies a single point site in the host, with the lowest C_1 symmetry. While for Pr and Nd x must be #<=#0.35, for smaller R ions, Sm to Yb, the phase appears for any x content. Detailed crystallographic data for BiErGeO_5 have been determined from the structure refinement of its neutron diffraction profile at room temperature. Optical absorption and photoluminescence measurements at 10 K have been performed for BiEuGeO_5. An initial approach to the parametrization of crystal-field effects on this new host has been provided by results of the semi-empirical Simple Overlap Model, which considers the crystallographic positions of the nearest neighbors around R. Furthermore, the strongly reduced "7F_J_M set of levels of the 4f"6 configuration has ...
In acute liver failure following hepatitis, toxic insults, or after major liver surgery, there is an increased bacterial translocation from the gut. This may explain some of the infectious complications seen in these conditions. To elucidate mechanisms and find possible preventive measures, we investigated the effect of rectal administration of arginine and probiotic bacteria (Lactobacillus spp.) on bacterial translocation and the extent of liver failure. Sprague-Dawley rats were used and five different Lactobacillus strains (Lb. reuteri R2LC, Lb. rhamnosus DSM 6594 (= strain 271), Lb. plantarum DSM 9843 (= strain 299v), Lb. fermentum 8704:3 (= strain 245), and Lb. reuteri (= strain 108) were administered rectally once daily for 8 days with and without 2% arginine. Acute liver injury (ALI) was induced on the eighth day by intraperitoneal injection of D-galactosamine (1.1 g/kg body weight), and samples were collected after 24 and 48 hours. Bacterial translocation was evaluated by ...
Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+ rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only ~0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are ...
The article focusses on operational experience gained with the following items: scrubbing system with oxidation, regenerative gas preheater, blower/fan, aerosol filter, and product processing. (orig./PW).
A study was made of the uncoupling action of polychlorinated biphenyls (Kanechlor-400) on oxidative phosphorylation in rat liver mitochondria. Kanechlor-400 (KC-400) at 20 ..mu..g/ml stimulated state 4 respiration of rat liver mitochondria more than 4-fold with ..cap alpha..-ketoglutarate/malate as a substrate, and released the oligomycin-inhibited state 3 respiration. KC-400 also dissipated the membrane potential across the mitochondrial membranes; thus, it acts as an uncoupler of oxidative phosphorylation in rat liver mitochondria. KC-400 altered the permeability properties of mitochondrial membranes as evidenced by the release of endogenous K/sup +/ and the oxidation of exogenously supplied NADH. It is concluded that KC-400 produces a nonspecific increase in mitochondrial ion permeability, thereby dissipating membrane potential, which leads to the uncoupling.
Metallic Zn films were deposited on glass substrates by electron-beam evaporation. ZnO films were synthesized by thermal oxidation of Zn metallic films in air. At the annealing temperature of 550 ?C, ZnO nanowires appeared on the surface, which mainly result from the decrease of oxidation rate. A ZnO ultraviolet photodetector was fabricated based on a metal-semiconductor-metal planar structure. The detector showed a large UV photoresponse with an increase of two orders of magnitude. It is concluded that promising UV detectors can be obtained on ZnO films by thermal oxidation of Zn metallic films. The ways of performing spectral response measurements for polycrystalline ZnO films are also discussed.
Dogs challenged with toxic doses of methylsalicylate developed acute myocardiopathy. Metabolic manifestations of uncoupling of oxidative phosphorylation by methylsalicylate (MS) were observed. Oxygen...Full Text Available
The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)
Senescence is regarded as a physiological response of cells to stress, including telomere dysfunction, aberrant oncogenic activation, DNA damage, and oxidative stress. This stress response has an antagonistically...Full Text Available
Pore Fraction in Yttrium-Barium-Copper-Oxide and. Other Polycrystalline. Materials ...... Properties of Yttrium Ceramic. Sov. J. LowTemp.Phys. 14:395-402 . ...
The objective of this project was to develop new photocatalytic or other innovative process chemistry for the treatment of pink water and related contaminated water.
Obesity is characterized by the abnormal or excessive deposition of fat in the adipose tissue. Its consequences go far beyond adverse metabolic effects on health, causing an increase in oxidative stress,...Full Text Available
A methodology for the determination of the rare earth elements in uranium oxides by ion microprobe has been set up on a Cameca ims-3f instrument. An uranium oxide reference material from a syn-metamorphic uranium deposit related to albitisation has also been developed for this type of analysis. Applications of the methodology are presented for a series of uranium oxides selected from some major uranium deposit types: from the world's highest grade unconformity-related uranium deposit from the Athabasca Basin (Saskatchewan, Canada; the Shea Creek and the McArthur River examples), a perigranitic vein-type deposit (Pen Ar Ran, Vendee, France) and a volcanic caldera-related deposit (Streltsovkoye, Transbaikalia, Russia). Each type of uranium deposit appears to have a specific REE signature. Al...
The nitric oxide molecule is being studied in order to understand the energetics and chemistry of initiation and detonation in liquid NO at the molecular level. An overview is presented of the work being done. (DLC)
familiarity fire triangle (i.e., fuel, oxidant, and ignition source) are excluded. It Is obvious that for the baseline safety goal for spacecraft this ...
High purity W and W-0.9La2O3 (wt.%) nanopowders were produced by a wet chemical route. The precursor was prepared by the reaction of ammonium paratungstate (APT) with lanthanum salt in aqueous solutions. High resolution electron microscopy investigations revealed that the tungstate particles were coated with oxide precipitates. The precursor powder was reduced to tungsten metal with dispersed lanthanum oxide. Powders were consolidated by spark plasma sintering (SPS) at 1300 and 1400degreeC to suppress grain growth during sintering. The final grain size relates to the SPS conditions, i.e. temperature and heating rate, regardless of the starting powder particle size. Scanning electron microscopy revealed that oxide phases were mainly accumulated at grain boundaries while the tungsten matrix ...
All of the direct reaction schemes described and the corresponding process schemes are still in an exploratory state. Ethylene by oxidative coupling of methane could become competitive if process schemes are developed with significantly less expenditures for separation of the product from unconverted feed. No encouragement for formaldehyde from methane can be presently derived from the existing knowledge. Liquid-phase oxidation of methane to methanol appears to be attractive but no final judgement is possible at present. Oxidative dehydrogenation of ethylene and propane look promising although further catalyst improvement is required. Acetic acid from ethane and acrylonitrile from propane have a certain potential as an alternative to present technology. The outlook for acrolein and acrylic acid from propane is less favourable; new concepts for catalyst design are necessary. (orig.)
Pulse reactor experiments were conducted on the reactions of unlabeled or deuterium- or oxygen-18-labeled allyl alcohols over molybdenum trioxide and various bismuth molybdates in the absence or presence of oxygen and ammonia. The allyl alcohol apparently adsorbed on oxidation sites to form acrolein via allyl molybdates, and on Broensted acid sites to form diallyl ether via an allyl carbonium ion. The bismuth enhanced ..cap alpha..-hydrogen abstraction, which was the rate-determining step in the oxidation. The product distributions provided evidence that the selective oxidation of propylene to acrolein proceeds via a m-allyl molybdate which collapses to an O o-allyl molybdate prior to the second hydrogen abstraction, and that the analogous N o-complex in ammoxidation undergoes two hydrogen abstractions to form acrylonitrile. Detailed reaction schemes are developed.
This project is concerned with the kinetics and mechanisms of aromatic oxidation and soot and fullerenes formation in flames. The objective of the aromatics oxidation work is to identify and measure the concentration of important intermediates and products in benzene oxidation, and to determine reaction mechanisms and kinetics properties consistent with the behavior seen in flames. The research on soot formation is concerned primarily with the particle inception stages, but the work includes study of soot structure at all stages of growth in order to obtain mechanistic information from evidence of growth steps recorded in the structure of the particles. The ultimate objective is to understand how nascent soot particles are formed from high molecular weight compounds, including the roles of planar and curved PAH and the relationship between soot and fullerenes. The objective of the proposed research on fullerenes is to ...
Hydrogen peroxide is a commonly used oxidizing agent with a variety of uses depending on its concentration. Ingestion of hydrogen peroxide is not an uncommon source of poisoning, and results in morbidity...Full Text Available