Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

Energy Technology Data Exchange (ETDEWEB)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi [Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I–35131 Padova, Italy and DEMOCRITOS National Simulation Center of the Italian Istituto Officina dei Materiali (IOM) of the Italian National Research Council (CNR), Trieste (Italy)

2016-03-21

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

International Nuclear Information System (INIS)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2016-01-01

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp 2 hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

Steam-chemical reactivity for irradiated beryllium

Energy Technology Data Exchange (ETDEWEB)

Anderl, R.A.; McCarthy, K.A.; Oates, M.A.; Petti, D.A.; Pawelko, R.J.; Smolik, G.R. [Idaho National Engineering and Environmental Lab., Idaho Falls, ID (United States)

1998-01-01

This paper reports the results of an experimental investigation to determine the influence of neutron irradiation effects and annealing on the chemical reactivity of beryllium exposed to steam. The work entailed measurements of the H{sub 2} generation rates for unirradiated and irradiated Be and for irradiated Be that had been previously annealed at different temperatures ranging from 450degC to 1200degC. H{sub 2} generation rates were similar for irradiated and unirradiated Be in steam-chemical reactivity experiments at temperatures between 450degC and 600degC. For irradiated Be exposed to steam at 700degC, the chemical reactivity accelerated rapidly and the specimen experienced a temperature excursion. Enhanced chemical reactivity at temperatures between 400degC and 600degC was observed for irradiated Be annealed at temperatures of 700degC and higher. This reactivity enhancement could be accounted for by the increased specific surface area resulting from development of a surface-connected porosity in the irradiated-annealed Be. (author)

Modelling of reactive fluid transport in deformable porous rocks

Science.gov (United States)

Yarushina, V. M.; Podladchikov, Y. Y.

2009-04-01

One outstanding challenge in geology today is the formulation of an understanding of the interaction between rocks and fluids. Advances in such knowledge are important for a broad range of geologic settings including partial melting and subsequent migration and emplacement of a melt into upper levels of the crust, or fluid flow during regional metamorphism and metasomatism. Rock-fluid interaction involves heat and mass transfer, deformation, hydrodynamic flow, and chemical reactions, thereby necessitating its consideration as a complex process coupling several simultaneous mechanisms. Deformation, chemical reactions, and fluid flow are coupled processes. Each affects the others. Special effort is required for accurate modelling of the porosity field through time. Mechanical compaction of porous rocks is usually treated under isothermal or isoentropic simplifying assumptions. However, joint consideration of both mechanical compaction and reactive porosity alteration requires somewhat greater than usual care about thermodynamic consistency. Here we consider the modelling of multi-component, multi-phase systems, which is fundamental to the study of fluid-rock interaction. Based on the conservation laws for mass, momentum, and energy in the form adopted in the theory of mixtures, we derive a thermodynamically admissible closed system of equations describing the coupling of heat and mass transfer, chemical reactions, and fluid flow in a deformable solid matrix. Geological environments where reactive transport is important are located at different depths and accordingly have different rheologies. In the near surface, elastic or elastoplastic properties would dominate, whereas viscoplasticity would have a profound effect deeper in the lithosphere. Poorly understood rheologies of heterogeneous porous rocks are derived from well understood processes (i.e., elasticity, viscosity, plastic flow, fracturing, and their combinations) on the microscale by considering a

Simulations of the dispersion of reactive pollutants in a street canyon, considering different chemical mechanisms and micromixing

Science.gov (United States)

Garmory, A.; Kim, I. S.; Britter, R. E.; Mastorakos, E.

The Stochastic Fields (SF) or Field Monte Carlo method has been used to model the dispersion of reactive scalars in a street canyon, using a simple chemistry and the CBM-IV mechanism. SF is a Probability Density Function (PDF) method which allows both means and variances of the scalars to be calculated as well as considering the effect of segregation on reaction rates. It was found that the variance of reactive scalars such as NO 2 was very high in the mixing region at roof-top level with rms values of the order of the mean values. The effect of segregation on major species such as O 3 was found to be very small using either mechanism, however, some radical species in CBM-IV showed a significant difference. These were found to be the seven species with the fastest chemical timescales. The calculated photostationary state defect was also found to be in error when segregation is neglected.

Numerical simulation of two-phase multicomponent flow with reactive transport in porous media

International Nuclear Information System (INIS)

Vostrikov, Viatcheslav

2014-01-01

The subject of this thesis is the numerical simulation of water-gas flow in the subsurface together with chemical reactions. The subject has applications to various situations in environmental modeling, though we are mainly concerned with CO 2 storage in deep saline aquifers. In Carbon Capture and Storage studies, CO 2 is first captured from its sources of origin, transport in liquefied form and injected as gas under high pressure in deep saline aquifers. Numerical simulation is an essential tool to make sure that gaseous CO 2 will remain trapped for several hundreds or thousands of years. Several trapping mechanisms can be brought to bear to achieve this goal. Of particular interest in this thesis are solubility trapping (whereby gaseous CO 2 dissolves in the brine as it moves upward) and, on a longer term, mineral trapping (which causes CO 2 to react with the surrounding rock to form minerals such as calcite). Thus, understanding how CO 2 reacts chemically becomes an important issue for its long term fate. The thesis is composed of four chapters. The first chapter is an introduction to multicomponent two-phase flow in porous media, with or without chemical reactions. It presents a review of the existing literature, and gives an outline of the whole thesis. Chapter 2 presents a quantitative discussion of the physical and chemical phenomena involved, and of their mathematical modeling. The model we use is that of two-phase two-component flow in porous media, coupled to reactive transport. This model leads to a large set of partial differential equations, coupled to algebraic equations, describing the evolution of the concentration of each species at each grid point. A direct solution of this problem (a fully coupled solution) is possible, but presents many difficulties form the numerical point of view. Moreover, it makes it difficult to reuse codes already written, and validated, to simulate the simpler phenomena of (uncoupled) two-phase flow and reactive transport

Chemical Reactivity Test (CRT)

Energy Technology Data Exchange (ETDEWEB)

Zaka, F. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2016-12-13

The Chemical Reactivity Test (CRT) is used to determine the thermal stability of High Explosives (HEs) and chemical compatibility between (HEs) and alien materials. The CRT is one of the small-scale safety tests performed on HE at the High Explosives Applications Facility (HEAF).

An autonomous organic reaction search engine for chemical reactivity

Science.gov (United States)

Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

2017-06-01

The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

Effect of 3-D moderator flow configurations on the reactivity of CANDU nuclear reactors

International Nuclear Information System (INIS)

Zadeh, Foad Mehdi; Etienne, Stephane; Chambon, Richard; Marleau, Guy; Teyssedou, Alberto

2017-01-01

Highlights: • 3-D CFD simulations of CANDU-6 moderator flows are presented. • A thermal-hydraulic code using thermal physical fluid properties is used. • The numerical approach and convergence is validated against available data. • Flow configurations are correlated using Richardson’s number. • The interaction between moderator temperatures with reactivity is determined. - Abstract: The reactivity of nuclear reactors can be affected by thermal conditions prevailing within the moderator. In CANDU reactors, the moderator and the coolant are mechanically separated but not necessarily thermally isolated. Hence, any variation of moderator flow properties may change the reactivity. Until now, nuclear reactor calculations have been performed by assuming uniform moderator flow temperature distribution. However, CFD simulations have predicted large time dependent flow fluctuations taking place inside the calandria, which can bring about local temperature variations that can exceed 50 °C. This paper presents robust CANDU 3-D CFD moderator simulations coupled to neutronic calculations. The proposed methodology makes it possible to study not only different moderator flow configurations but also their effects on the reactor reactivity coefficient.

Numerical Simulation of Reactive Flows in Overexpanded Supersonic Nozzle with Film Cooling

Directory of Open Access Journals (Sweden)

Mohamed Sellam

2015-01-01

Full Text Available Reignition phenomena occurring in a supersonic nozzle flow may present a crucial safety issue for rocket propulsion systems. These phenomena concern mainly rocket engines which use H2 gas (GH2 in the film cooling device, particularly when the nozzle operates under over expanded flow conditions at sea level or at low altitudes. Consequently, the induced wall thermal loads can lead to the nozzle geometry alteration, which in turn, leads to the appearance of strong side loads that may be detrimental to the rocket engine structural integrity. It is therefore necessary to understand both aerodynamic and chemical mechanisms that are at the origin of these processes. This paper is a numerical contribution which reports results from CFD analysis carried out for supersonic reactive flows in a planar nozzle cooled with GH2 film. Like the experimental observations, CFD simulations showed their ability to highlight these phenomena for the same nozzle flow conditions. Induced thermal load are also analyzed in terms of cooling efficiency and the results already give an idea on their magnitude. It was also shown that slightly increasing the film injection pressure can avoid the reignition phenomena by moving the separation shock towards the nozzle exit section.

Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

Energy Technology Data Exchange (ETDEWEB)

Magnussen, B F [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

1998-12-31

The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

Energy Technology Data Exchange (ETDEWEB)

Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

1997-12-31

The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

Reactive Ion Etching as Cleaning Method Post Chemical Mechanical Polishing for Phase Change Memory Device

International Nuclear Information System (INIS)

Min, Zhong; Zhi-Tang, Song; Bo, Liu; Song-Lin, Feng; Bomy, Chen

2008-01-01

In order to improve nano-scale phase change memory performance, a super-clean interface should be obtained after chemical mechanical polishing (CMP) of Ge 2 Sb 2 Te 5 phase change films. We use reactive ion etching (RIE) as the cleaning method. The cleaning effect is analysed by scanning electron microscopy and an energy dispersive spectrometer. The results show that particle residue on the surface has been removed. Meanwhile, Ge 2 Sb 2 Te 5 material stoichiometric content ratios are unchanged. After the top electrode is deposited, current-voltage characteristics test demonstrates that the set threshold voltage is reduced from 13 V to 2.7V and the threshold current from 0.1mA to 0.025mA. Furthermore, we analyse the RIE cleaning principle and compare it with the ultrasonic method

Reactive chemicals and process hazards

International Nuclear Information System (INIS)

Surianarayanan, M.

2016-01-01

Exothermic chemical reactions are often accompanied by significant heat release, and therefore, need a thorough investigation before they are taken to a plant scale. Sudden thermal energy releases from exothermic decompositions and runaway reactions have contributed to serious fire and explosions in several chemical process plants. Similarly, thermal runaway had also occurred in storage and transportation of reactive chemicals. The secondary events of thermal runaway reactions can be rupture of process vessel, toxic spills and release of explosive vapor clouds or combination of these also. The explosion hazards are governed by the system thermodynamics and kinetics of the thermal process. Theoretical prediction of limiting temperature is difficult due to process complexities. Further, the kinetic data obtained through classical techniques, at conditions far away from runaway situation, is often not valid for assessing the runaway behavior of exothermic processes. The main focus of this lecture is to discuss the causes and several contributing factors for thermal runaway and instability and present analyses of the methodologies of the new instrumental techniques for assessing the thermal hazards of reactive chemicals during processing, storage and transportation. (author)

On Variable Reverse Power Flow-Part I: Active-Reactive Optimal Power Flow with Reactive Power of Wind Stations

Directory of Open Access Journals (Sweden)

Aouss Gabash

2016-02-01

Full Text Available It has recently been shown that using battery storage systems (BSSs to provide reactive power provision in a medium-voltage (MV active distribution network (ADN with embedded wind stations (WSs can lead to a huge amount of reverse power to an upstream transmission network (TN. However, unity power factors (PFs of WSs were assumed in those studies to analyze the potential of BSSs. Therefore, in this paper (Part-I, we aim to further explore the pure reactive power potential of WSs (i.e., without BSSs by investigating the issue of variable reverse power flow under different limits on PFs in an electricity market model. The main contributions of this work are summarized as follows: (1 Introducing the reactive power capability of WSs in the optimization model of the active-reactive optimal power flow (A-R-OPF and highlighting the benefits/impacts under different limits on PFs. (2 Investigating the impacts of different agreements for variable reverse power flow on the operation of an ADN under different demand scenarios. (3 Derivation of the function of reactive energy losses in the grid with an equivalent-π circuit and comparing its value with active energy losses. (4 Balancing the energy curtailment of wind generation, active-reactive energy losses in the grid and active-reactive energy import-export by a meter-based method. In Part-II, the potential of the developed model is studied through analyzing an electricity market model and a 41-bus network with different locations of WSs.

Thermal/chemical degradation of ceramic cross-flow filter materials

Energy Technology Data Exchange (ETDEWEB)

Alvin, M.A.; Lane, J.E.; Lippert, T.E.

1989-11-01

This report summarizes the 14-month, Phase 1 effort conducted by Westinghouse on the Thermal/Chemical Degradation of Ceramic Cross-Flow Filter Materials program. In Phase 1 expected filter process conditions were identified for a fixed-bed, fluid-bed, and entrained-bed gasification, direct coal fired turbine, and pressurized fluidized-bed combustion system. Ceramic cross-flow filter materials were also selected, procured, and subjected to chemical and physical characterization. The stability of each of the ceramic cross-flow materials was assessed in terms of potential reactions or phase change as a result of process temperature, and effluent gas compositions containing alkali and fines. In addition chemical and physical characterization was conducted on cross-flow filters that were exposed to the METC fluid-bed gasifier and the New York University pressurized fluidized-bed combustor. Long-term high temperature degradation mechanisms were proposed for each ceramic cross-flow material at process operating conditions. An experimental bench-scale test program is recommended to be conducted in Phase 2, generating data that support the proposed cross-flow filter material thermal/chemical degradation mechanisms. Papers on the individual subtasks have been processed separately for inclusion on the data base.

Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem

KAUST Repository

Nick, H.M.

2013-02-01

The reactive mixing between seawater and terrestrial water in coastal aquifers influences the water quality of submarine groundwater discharge. While these waters come into contact at the seawater groundwater interface by density driven flow, their chemical components dilute and react through dispersion. A larger interface and wider mixing zone may provide favorable conditions for the natural attenuation of contaminant plumes. It has been claimed that the extent of this mixing is controlled by both, porous media properties and flow conditions. In this study, the interplay between dispersion and reactive processes in coastal aquifers is investigated by means of numerical experiments. Particularly, the impact of dispersion coefficients, the velocity field induced by density driven flow and chemical component reactivities on reactive transport in such aquifers is studied. To do this, a hybrid finite-element finite-volume method and a reactive simulator are coupled, and model accuracy and applicability are assessed. A simple redox reaction is considered to describe the degradation of a contaminant which requires mixing of the contaminated groundwater and the seawater containing the terminal electron acceptor. The resulting degradation is observed for different scenarios considering different magnitudes of dispersion and chemical reactivity. Three reactive transport regimes are found: reaction controlled, reaction-dispersion controlled and dispersion controlled. Computational results suggest that the chemical components\\' reactivity as well as dispersion coefficients play a significant role on controlling reactive mixing zones and extent of contaminant removal in coastal aquifers. Further, our results confirm that the dilution index is a better alternative to the second central spatial moment of a plume to describe the mixing of reactive solutes in coastal aquifers. © 2012 Elsevier B.V.

Direct numerical simulation of turbulent, chemically reacting flows

Science.gov (United States)

Doom, Jeffrey Joseph

This dissertation: (i) develops a novel numerical method for DNS/LES of compressible, turbulent reacting flows, (ii) performs several validation simulations, (iii) studies auto-ignition of a hydrogen vortex ring in air and (iv) studies a hydrogen/air turbulent diffusion flame. The numerical method is spatially non-dissipative, implicit and applicable over a range of Mach numbers. The compressible Navier-Stokes equations are rescaled so that the zero Mach number equations are discretely recovered in the limit of zero Mach number. The dependent variables are co--located in space, and thermodynamic variables are staggered from velocity in time. The algorithm discretely conserves kinetic energy in the incompressible, inviscid, non--reacting limit. The chemical source terms are implicit in time to allow for stiff chemical mechanisms. The algorithm is readily applicable to complex chemical mechanisms. Good results are obtained for validation simulations. The algorithm is used to study auto-ignition in laminar vortex rings. A nine species, nineteen reaction mechanism for H2/air combustion proposed by Mueller et al. [37] is used. Diluted H 2 at ambient temperature (300 K) is injected into hot air. The simulations study the effect of fuel/air ratio, oxidizer temperature, Lewis number and stroke ratio (ratio of piston stroke length to diameter). Results show that auto--ignition occurs in fuel lean, high temperature regions with low scalar dissipation at a 'most reactive' mixture fraction, zeta MR (Mastorakos et al. [32]). Subsequent evolution of the flame is not predicted by zetaMR; a most reactive temperature TMR is defined and shown to predict both the initial auto-ignition as well as subsequent evolution. For stroke ratios less than the formation number, ignition in general occurs behind the vortex ring and propagates into the core. At higher oxidizer temperatures, ignition is almost instantaneous and occurs along the entire interface between fuel and oxidizer. For stroke

Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

Science.gov (United States)

Wang, XinJie; Wu, YanQing; Huang, FengLei

2017-01-05

A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Stability Analysis of Reactive Multiphase Slug Flows in Microchannels

Directory of Open Access Journals (Sweden)

Alejandro A. Munera Parra

2014-05-01

Full Text Available Conducting multiphase reactions in micro-reactors is a promising strategy for intensifying chemical and biochemical processes. A major unresolved challenge is to exploit the considerable benefits offered by micro-scale operation for industrial scale throughputs by numbering-up whilst retaining the underlying advantageous flow characteristics of the single channel system in multiple parallel channels. Fabrication and installation tolerances in the individual micro-channels result in different pressure losses and, thus, a fluid maldistribution. In this work, an additional source of maldistribution, namely the flow multiplicities, which can arise in a multiphase reactive or extractive flow in otherwise identical micro-channels, was investigated. A detailed experimental and theoretical analysis of the flow stability with and without reaction for both gas-liquid and liquid-liquid slug flow has been developed. The model has been validated using the extraction of acetic acid from n-heptane with the ionic liquid 1-Ethyl-3-methylimidazolium ethyl sulfate. The results clearly demonstrate that the coupling between flow structure, the extent of reaction/extraction and pressure drop can result in multiple operating states, thus, necessitating an active measurement and control concept to ensure uniform behavior and optimal performance.

Upscaling of reactive flows

NARCIS (Netherlands)

Kumar, K.

2012-01-01

The thesis deals with the upscaling of reactive flows in complex geometry. The reactions which may include deposition or dissolution take place at a part of the boundary and depending on the size of the reaction domain, the changes in the pore structure that are due to the deposition process may or

Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

International Nuclear Information System (INIS)

Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

2014-01-01

This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application.

Science.gov (United States)

Vabbilisetty, Pratima; Boron, Mallorie; Nie, Huan; Ozhegov, Evgeny; Sun, Xue-Long

2018-02-28

Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell's functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine-poly(ethylene glycol)-dibenzocyclooctyne (DSPE-PEG 2000 -DBCO) and cholesterol-PEG-dibenzocyclooctyne (CHOL-PEG 2000 -DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids.

Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application

Science.gov (United States)

2018-01-01

Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell’s functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine–poly(ethylene glycol)–dibenzocyclooctyne (DSPE–PEG2000–DBCO) and cholesterol–PEG–dibenzocyclooctyne (CHOL–PEG2000–DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids. PMID:29503972

Numerical solution of chemically reactive non-Newtonian fluid flow: Dual stratification

Science.gov (United States)

Rehman, Khalil Ur; Malik, M. Y.; Khan, Abid Ali; Zehra, Iffat; Zahri, Mostafa; Tahir, M.

2017-12-01

We have found that only a few attempts are available in the literature relatively to the tangent hyperbolic fluid flow induced by stretching cylindrical surfaces. In particular, temperature and concentration stratification effects have not been investigated until now with respect to the tangent hyperbolic fluid model. Therefore, we have considered the tangent hyperbolic fluid flow induced by an acutely inclined cylindrical surface in the presence of both temperature and concentration stratification effects. To be more specific, the fluid flow is attained with the no slip condition, which implies that the bulk motion of the fluid particles is the same as the stretching velocity of a cylindrical surface. Additionally, the flow field situation is manifested with heat generation, mixed convection and chemical reaction effects. The flow partial differential equations give a complete description of the present problem. Therefore, to trace out the solution, a set of suitable transformations is introduced to convert these equations into ordinary differential equations. In addition, a self-coded computational algorithm is executed to inspect the numerical solution of these reduced equations. The effect logs of the involved parameters are provided graphically. Furthermore, the variations of the physical quantities are examined and given with the aid of tables. It is observed that the fluid temperature is a decreasing function of the thermal stratification parameter and a similar trend is noticed for the concentration via the solutal stratification parameter.

Reactive skin decontamination lotion (RSDL) for the decontamination of chemical warfare agent (CWA) dermal exposure.

Science.gov (United States)

Schwartz, M D; Hurst, C G; Kirk, M A; Reedy, S J D; Braue, E H

2012-08-01

Rapid decontamination of the skin is the single most important action to prevent dermal absorption of chemical contaminants in persons exposed to chemical warfare agents (CWA) and toxic industrial chemicals (TICs) as a result of accidental or intentional release. Chemicals on the skin may be removed by mechanical means through the use of dry sorbents or water. Recent interest in decontamination systems which both partition contaminants away from the skin and actively neutralize the chemical has led to the development of several reactive decontamination solutions. This article will review the recently FDA-approved Reactive Skin Decontamination Lotion (RSDL) and will summarize the toxicity and efficacy studies conducted to date. Evidence of RSDL's superior performance against vesicant and organophosphorus chemical warfare agents compared to water, bleach, and dry sorbents, suggests that RSDL may have a role in mass human exposure chemical decontamination in both the military and civilian arenas.

Automated chemical kinetic modeling via hybrid reactive molecular dynamics and quantum chemistry simulations.

Science.gov (United States)

Döntgen, Malte; Schmalz, Felix; Kopp, Wassja A; Kröger, Leif C; Leonhard, Kai

2018-06-13

An automated scheme for obtaining chemical kinetic models from scratch using reactive molecular dynamics and quantum chemistry simulations is presented. This methodology combines the phase space sampling of reactive molecular dynamics with the thermochemistry and kinetics prediction capabilities of quantum mechanics. This scheme provides the NASA polynomial and modified Arrhenius equation parameters for all species and reactions that are observed during the simulation and supplies them in the ChemKin format. The ab initio level of theory for predictions is easily exchangeable and the presently used G3MP2 level of theory is found to reliably reproduce hydrogen and methane oxidation thermochemistry and kinetics data. Chemical kinetic models obtained with this approach are ready-to-use for, e.g., ignition delay time simulations, as shown for hydrogen combustion. The presented extension of the ChemTraYzer approach can be used as a basis for methodologically advancing chemical kinetic modeling schemes and as a black-box approach to generate chemical kinetic models.

Large-Eddy Simulation of Chemically Reactive Pollutant Transport from a Point Source in Urban Area

Science.gov (United States)

Du, Tangzheng; Liu, Chun-Ho

2013-04-01

Most air pollutants are chemically reactive so using inert scalar as the tracer in pollutant dispersion modelling would often overlook their impact on urban inhabitants. In this study, large-eddy simulation (LES) is used to examine the plume dispersion of chemically reactive pollutants in a hypothetical atmospheric boundary layer (ABL) in neutral stratification. The irreversible chemistry mechanism of ozone (O3) titration is integrated into the LES model. Nitric oxide (NO) is emitted from an elevated point source in a rectangular spatial domain doped with O3. The LES results are compared well with the wind tunnel results available in literature. Afterwards, the LES model is applied to idealized two-dimensional (2D) street canyons of unity aspect ratio to study the behaviours of chemically reactive plume over idealized urban roughness. The relation among various time scales of reaction/turbulence and dimensionless number are analysed.

Chemically reactive and naturally convective high speed MHD fluid flow through an oscillatory vertical porous plate with heat and radiation absorption effect

Directory of Open Access Journals (Sweden)

S.M. Arifuzzaman

2018-04-01

Full Text Available This paper concerns with the modelling of an unsteady natural convective and higher order chemically reactive magnetohydrodynamics (MHD fluid flow with the effect of heat and radiation absorption. The flow is generated through a vertical oscillating porous plate. Boundary layer approximations is carried out to establish a flow model which represents the time dependent momentum, energy and diffusion balance equations. Before being solved numerically, the governing partial differential equations (PDEs were transformed into a set of nonlinear ordinary differential equation (ODEs by using non-similar technique. A very efficient numerical approach solves the obtained nonlinear coupled ODEs so called Explicit Finite Difference Method (EFDM. An algorithm is implemented in Compaq Visual Fortran 6.6a as a solving tool. In addition, the stability and convergence analysis (SCA is examined and shown explicitly. The advantages of SCA is its optimizes the accuracy of system parameters such as Prandtl number (Pr and Schmidt number (Sc.The velocity, temperature and concentration fields in the boundary layer region are studied in detail and the outcomes are shown in graphically with the influence of various pertinent parameters such as Grashof number (Gr, modified Grashof number (Gr, magnetic parameter (M, Darcy number (Da,Prandtl number (Pr, Schmidt number (Sc, radiation (R, heat sink (Q,radiation absorption (Q1, Eckert number (Ec, Dufour number (Du,Soret number (Sr, Schmidt number (Sc, reaction index (P and chemical reaction (Kr. Furthermore, the effect of skin friction coefficient (Cf, Nusselt number (Nu and Sherwood number (Sh are also examined graphically. Keywords: MHD, Oscillating porous plate, Radiation absorption, High order chemical reaction, EFDM

PDF methods for turbulent reactive flows

Science.gov (United States)

Hsu, Andrew T.

1995-01-01

Viewgraphs are presented on computation of turbulent combustion, governing equations, closure problem, PDF modeling of turbulent reactive flows, validation cases, current projects, and collaboration with industry and technology transfer.

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

International Nuclear Information System (INIS)

Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

2007-01-01

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

Science.gov (United States)

Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

2007-06-16

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

Generalized Riemann problem for reactive flows

International Nuclear Information System (INIS)

Ben-Artzi, M.

1989-01-01

A generalized Riemann problem is introduced for the equations of reactive non-viscous compressible flow in one space dimension. Initial data are assumed to be linearly distributed on both sides of a jump discontinuity. The resolution of the singularity is studied and the first-order variation (in time) of flow variables is given in exact form. copyright 1989 Academic Press, Inc

Flow of chemically reactive magneto Cross nanoliquid with temperature-dependent conductivity

Science.gov (United States)

Hayat, Tasawar; Ullah, Ikram; Waqas, Muhammad; Alsaedi, Ahmed

2018-05-01

Influence of temperature-dependent thermal conductivity on MHD flow of Cross nanoliquid bounded by a stretched sheet is explored. The combined feature of Brownian motion and thermophoresis in nanoliquid modeling is retained. In addition, the attributes of zero mass flux at sheet are imposed. First-order chemical reaction is retained. The resulting problems are numerically computed. Plots and tabulated values are presented and examined. It is figured out that larger thermophoretic diffusion and thermal conductivity significantly rise the thermal field, whereas opposite situation is seen for heat transfer rate.

Influence of Chemical, Mechanical, and Transport Processes on Wellbore Leakage from Geologic CO2 Storage Reservoirs.

Science.gov (United States)

Carroll, Susan A; Iyer, Jaisree; Walsh, Stuart D C

2017-08-15

Wells are considered to be high-risk pathways for fluid leakage from geologic CO 2 storage reservoirs, because breaches in this engineered system have the potential to connect the reservoir to groundwater resources and the atmosphere. Given these concerns, a few studies have assessed leakage risk by evaluating regulatory records, often self-reported, documenting leakage in gas fields. Leakage is thought to be governed largely by initial well-construction quality and the method of well abandonment. The geologic carbon storage community has raised further concerns because acidic fluids in the CO 2 storage reservoir, alkaline cement meant to isolate the reservoir fluids from the overlying strata, and steel casings in wells are inherently reactive systems. This is of particular concern for storage of CO 2 in depleted oil and gas reservoirs with numerous legacy wells engineered to variable standards. Research suggests that leakage risks are not as great as initially perceived because chemical and mechanical alteration of cement has the capacity to seal damaged zones. Our work centers on defining the coupled chemical and mechanical processes governing flow in damaged zones in wells. We have developed process-based models, constrained by experiments, to better understand and forecast leakage risk. Leakage pathways can be sealed by precipitation of carbonate minerals in the fractures and deformation of the reacted cement. High reactivity of cement hydroxides releases excess calcium that can precipitate as carbonate solids in the fracture network under low brine flow rates. If the flow is fast, then the brine remains undersaturated with respect to the solubility of calcium carbonate minerals, and zones depleted in calcium hydroxides, enriched in calcium carbonate precipitates, and made of amorphous silicates leached of original cement minerals are formed. Under confining pressure, the reacted cement is compressed, which reduces permeability and lowers leakage risks. The

Numerical simulations of heterogeneous chemical reactions coupled to fluid flow in varying thermal fields

International Nuclear Information System (INIS)

Carnahan, C.L.

1991-11-01

A numerical simulator of reactive chemical transport with coupling from precipitation-dissolution reactions to fluid flow, via changes of porosity and permeability, is applied to precipitation-dissolution of quartz and calcite in spatially and temporally variable fields of temperature. Significant effects on fluid flow are found in the quartz-silicic acid system in the presence of persistent, strong gradient of temperature. Transient heat flow in the quartz-silicic acid system and in a calcite-calcium ion-carbonato species system produces vanishingly small effects on fluid flow

Hybrid finite-volume/transported PDF method for the simulation of turbulent reactive flows

Science.gov (United States)

Raman, Venkatramanan

A novel computational scheme is formulated for simulating turbulent reactive flows in complex geometries with detailed chemical kinetics. A Probability Density Function (PDF) based method that handles the scalar transport equation is coupled with an existing Finite Volume (FV) Reynolds-Averaged Navier-Stokes (RANS) flow solver. The PDF formulation leads to closed chemical source terms and facilitates the use of detailed chemical mechanisms without approximations. The particle-based PDF scheme is modified to handle complex geometries and grid structures. Grid-independent particle evolution schemes that scale linearly with the problem size are implemented in the Monte-Carlo PDF solver. A novel algorithm, in situ adaptive tabulation (ISAT) is employed to ensure tractability of complex chemistry involving a multitude of species. Several non-reacting test cases are performed to ascertain the efficiency and accuracy of the method. Simulation results from a turbulent jet-diffusion flame case are compared against experimental data. The effect of micromixing model, turbulence model and reaction scheme on flame predictions are discussed extensively. Finally, the method is used to analyze the Dow Chlorination Reactor. Detailed kinetics involving 37 species and 158 reactions as well as a reduced form with 16 species and 21 reactions are used. The effect of inlet configuration on reactor behavior and product distribution is analyzed. Plant-scale reactors exhibit quenching phenomena that cannot be reproduced by conventional simulation methods. The FV-PDF method predicts quenching accurately and provides insight into the dynamics of the reactor near extinction. The accuracy of the fractional time-stepping technique in discussed in the context of apparent multiple-steady states observed in a non-premixed feed configuration of the chlorination reactor.

The study of mechanical properties and reactive stresses in the i-Ni-Nb shape memory alloys

International Nuclear Information System (INIS)

Popov, N.N.; Sysoeva, T.I.; Lar'kin, V.F.; Vedernikova, I.I.; Prokoshkin, S.D.

2007-01-01

One investigated into the effect of the induced deformation value, rate and temperature, of the thermal treatment procedure and of the chemical composition on the mechanical properties and the development of the reactive stresses in Ti-Ni-Nb system shape memory alloys. One showed the effect of the material composition and of the deformation temperature on the mechanical features of the investigated alloys. One determined the temperature and deformation conditions ensuring the maximum level of the reactive stresses in the alloys. One revealed the dependence of the maximum reactive stress value on the austenite mechanical features, namely, on its yield limit. One chose Ti-Ni-Nb alloy compositions applicable in the pipeline thermomechanical connections [ru

Development of a Thermo-chemical Non-equilibrium Solver for Hypervelocity Flows

Science.gov (United States)

Balasubramanian, R.; Anandhanarayanan, K.

2015-04-01

In the present study, a three dimensional flowsolver is indigenously developed to numerically simulate hypervelocity thermal and chemical non equilibrium reactive air flow past flight vehicles. The two-temperature, five species, seventeen reactions, thermo-chemical non equilibrium, non-ionizing, air-chemistry model of Park is implemented in a compressible viscous code CERANS and solved in the finite volume framework. The energy relaxation is addressed by a conservation equation for the vibrational energy of the gas mixture resulting in the evaluation of its vibrational temperature. The AUSM-PW+ numerical flux function has been used for modeling the convective fluxes and a central differencing approximation is used for modeling the diffusive fluxes. The flowsolver had been validated for specifically chosen test cases with inherent flow complexities of non-ionizing hypervelocity thermochemical nonequilibrium flows and results obtained are in good agreement with results available in open literature.

The chemical reactivity and structure of collagen studied by neutron diffraction

Energy Technology Data Exchange (ETDEWEB)

Wess, T.J.; Wess, L.; Miller, A. [Univ. of Stirling (United Kingdom)

1994-12-31

The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon.

The chemical reactivity and structure of collagen studied by neutron diffraction

International Nuclear Information System (INIS)

Wess, T.J.; Wess, L.; Miller, A.

1994-01-01

The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon

Modeling food matrix effects on chemical reactivity: Challenges and perspectives.

Science.gov (United States)

Capuano, Edoardo; Oliviero, Teresa; van Boekel, Martinus A J S

2017-06-29

The same chemical reaction may be different in terms of its position of the equilibrium (i.e., thermodynamics) and its kinetics when studied in different foods. The diversity in the chemical composition of food and in its structural organization at macro-, meso-, and microscopic levels, that is, the food matrix, is responsible for this difference. In this viewpoint paper, the multiple, and interconnected ways the food matrix can affect chemical reactivity are summarized. Moreover, mechanistic and empirical approaches to explain and predict the effect of food matrix on chemical reactivity are described. Mechanistic models aim to quantify the effect of food matrix based on a detailed understanding of the chemical and physical phenomena occurring in food. Their applicability is limited at the moment to very simple food systems. Empirical modeling based on machine learning combined with data-mining techniques may represent an alternative, useful option to predict the effect of the food matrix on chemical reactivity and to identify chemical and physical properties to be further tested. In such a way the mechanistic understanding of the effect of the food matrix on chemical reactions can be improved.

6th International Workshop on Model Reduction in Reactive Flow

Science.gov (United States)

2018-01-01

reduction in reacting flow . Registration DateRegistration TypeFirst Name Middle NameLast Name Affiliation US State /Canadian ProvinceState/Province/R gion...Report: 6th International Workshop on Model Reduction in Reactive Flow The views, opinions and/or findings contained in this report are those of the...Agreement Number: W911NF-17-1-0121 Organization: Princeton University Title: 6th International Workshop on Model Reduction in Reactive Flow Report Term

Study on chemical reactivity control of liquid sodium. Research program

International Nuclear Information System (INIS)

Saito, Jun-ichi; Ara, Kuniaki; Sugiyama, Ken-ichiro; Kitagawa, Hiroshi; Oka, Nobuki; Yoshioka, Naoki

2007-01-01

Liquid sodium has the excellent properties as coolant of the fast breeder reactor (FBR). On the other hand, it reacts high with water and oxygen. So an innovative technology to suppress the reactivity is desired. The purpose of this study is to control the chemical reactivity of liquid sodium by dispersing the nanometer-size metallic particles (we call them Nano-particles) into liquid sodium. We focus on the atomic interaction between Nano-particles and sodium atoms. And we try to apply it to suppress the chemical reactivity of liquid sodium. Liquid sodium dispersing Nano-particles is named 'Nano-fluid'. Research programs of this study are the Nano-particles production, the evaluation of reactivity suppression of liquid sodium and the feasibility study to FBR plant. In this paper, the research programs and status are described. The important factors for particle production were understood. In order to evaluate the chemical reactivity of Nano-fluid the research programs were planned. The feasibility of the application of Nano-fluid to the coolant of FBR plant was evaluated preliminarily from the viewpoint of design and operation. (author)

Phase rule calculations and the thermodynamics of reactive systems under chemical equilibrium

Directory of Open Access Journals (Sweden)

PLATT G. M.

1999-01-01

Full Text Available In this paper, we examine the resolution of some phase rule problems within the context of multiple chemical equilibrium reactions, using cubic equations of state and an activity coefficient model. Bubble and dew reactive surfaces, reactive azeotropic loci and reactive critical loci are generated and presented in graphical form. Also isobaric bubble and dew reactive enthalpy loci, which may be useful in the modeling of reactive distillation operations, are depicted. All the formalism here employed is developed within the coordinate transformation of Ung and Doherty, which is appropriate for equilibrium reactive or multireactive systems. The major contribution of this work is the determination of critical loci for reactive or multireactive equilibrium systems. Since it is known that for some class of chemical reactions the kinetics and product distribution exhibit high sensitivity to pressure near criticality, the present study may be useful as a predicting tool in these cases if the chemical equilibrium condition is not too far from the real phenomenon.

CONCHAS-SPRAY, Reactive Flows with Fuel Sprays

International Nuclear Information System (INIS)

Cloutman, L.D.; Dukowicz, J.K.; Ramshaw, J.D.; Amsden, A.A.

2001-01-01

Description of program or function: CONCHAS-SPRAY solves the equations of transient, multicomponent, chemically reactive fluid dynamics, together with those for the dynamics of an evaporating liquid spray. The program was developed with applications to internal combustion engines in mind. The formulation is spatially two-dimensional, and encompasses both planar and axisymmetric geometries. In the latter case, the flow is permitted to swirl about the axis of symmetry. CONCHAS-SPRAY is a time-marching, finite- difference program that uses a partially implicit numerical scheme. Spatial differences are formed with respect to a generalized two- dimensional mesh of arbitrary quadrilaterals whose corner locations are specified functions of time. This feature allows a Lagrangian, Eulerian, or mixed description, and is particularly useful for representing curved or moving boundary surfaces. Arbitrary numbers of species and chemical reactions are allowed. The latter are subdivided into kinetic and equilibrium reactions, which are treated by different algorithms. A turbulent law-of-the-wall boundary layer option is provided. CONCHAS-SPRAY calls a number of LANL system subroutines to display graphic or numerical information on microfiche. These routines are not included, but are described in the reference report. Several routines called from LINPACK and SLATEC1.0 are included

Theoretical study of some aspects of the nucleo-bases reactivity: definition of new theoretical tools for the study of chemical reactivity

International Nuclear Information System (INIS)

Labet, V.

2009-09-01

In this work, three kinds of nucleo-base damages were studied from a theoretical point of view with quantum chemistry methods based on the density-functional theory: the spontaneous deamination of cytosine and its derivatives, the formation of tandem lesion induced by hydroxyl radicals in anaerobic medium and the formation of pyrimidic dimers under exposition to an UV radiation. The complementary use of quantitative static methods allowing the exploration of the potential energy surface of a chemical reaction, and of 'conceptual DFT' principles, leads to information concerning the mechanisms involved and to the rationalization of the differences in the nucleo-bases reactivity towards the formation of a same kind of damage. At the same time, a reflexion was undertaken on the asynchronous concerted mechanism concept, in terms of physical meaning of the transition state, respect of the Maximum Hardness Principle, and determination of the number of primitive processes involved. Finally, a new local reactivity index was developed, relevant to understand the reactivity of a molecular system in an excited state. (author)

A heuristic technique to determine corrective control actions for reactive power flows

Energy Technology Data Exchange (ETDEWEB)

Trigo, Angel L.; Martinez, Jose L.; Riquelme, Jesus; Romero, Esther [Department of Electrical Engineering, University of Sevilla (Spain)

2011-01-15

This paper presents a sensitivity-based heuristic tool designed to help the system operator in the reactive power flow control problem. The objective of the proposed technique is to determine control actions to ensure that reactive power flows in transmission-subtransmission boundary transformers remain within specified limits, satisfying the new regulatory constraints imposed in most of deregulated markets. With this new constraint the utilities want to guarantee that the utility is able to satisfy its own reactive power requirements, avoiding reactive power flows through long distances in order to reduce the well known disadvantages that reactive power circulation has in the system. A 5-bus tutorial system is used to present the proposed algorithm. The results of the application of the proposed technique to the IEEE 118 buses system and to a regional subtransmission network of the South of Spain are reported and analyzed. In this last actual case, the aim is to maintain reactive power flows in transmission/distribution transformers between those limits set by the Spanish Regulation. A comparison between the proposed tool and a conventional OPF is discussed. (author)

Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

Science.gov (United States)

Zhang, Wei; Huang, Guangming

2015-11-15

Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

Reactivity of Dual-Use Decontaminants with Chemical Warfare Agents

Science.gov (United States)

2016-07-01

REACTIVITY OF DUAL-USE DECONTAMINANTS WITH CHEMICAL WARFARE AGENTS ECBC-TR-1384... Decontaminants with Chemical Warfare Agents 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Willis, Matthew P...extraction) of chemical warfare agents from materials. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent Liquid-phase

Structure-mechanism-based engineering of chemical regulators targeting distinct pathological factors in Alzheimer's disease.

Science.gov (United States)

Beck, Michael W; Derrick, Jeffrey S; Kerr, Richard A; Oh, Shin Bi; Cho, Woo Jong; Lee, Shin Jung C; Ji, Yonghwan; Han, Jiyeon; Tehrani, Zahra Aliakbar; Suh, Nayoung; Kim, Sujeong; Larsen, Scott D; Kim, Kwang S; Lee, Joo-Yong; Ruotolo, Brandon T; Lim, Mi Hee

2016-10-13

The absence of effective therapeutics against Alzheimer's disease (AD) is a result of the limited understanding of its multifaceted aetiology. Because of the lack of chemical tools to identify pathological factors, investigations into AD pathogenesis have also been insubstantial. Here we report chemical regulators that demonstrate distinct specificity towards targets linked to AD pathology, including metals, amyloid-β (Aβ), metal-Aβ, reactive oxygen species, and free organic radicals. We obtained these chemical regulators through a rational structure-mechanism-based design strategy. We performed structural variations of small molecules for fine-tuning their electronic properties, such as ionization potentials and mechanistic pathways for reactivity towards different targets. We established in vitro and/or in vivo efficacies of the regulators for modulating their targets' reactivities, ameliorating toxicity, reducing amyloid pathology, and improving cognitive deficits. Our chemical tools show promise for deciphering AD pathogenesis and discovering effective drugs.

A Chemo-Mechanical Model of Diffusion in Reactive Systems

Directory of Open Access Journals (Sweden)

Kerstin Weinberg

2018-02-01

Full Text Available The functional properties of multi-component materials are often determined by a rearrangement of their different phases and by chemical reactions of their components. In this contribution, a material model is presented which enables computational simulations and structural optimization of solid multi-component systems. Typical Systems of this kind are anodes in batteries, reactive polymer blends and propellants. The physical processes which are assumed to contribute to the microstructural evolution are: (i particle exchange and mechanical deformation; (ii spinodal decomposition and phase coarsening; (iii chemical reactions between the components; and (iv energetic forces associated with the elastic field of the solid. To illustrate the capability of the deduced coupled field model, three-dimensional Non-Uniform Rational Basis Spline (NURBS based finite element simulations of such multi-component structures are presented.

The synergistic effect of chemical carcinogens enhances Epstein-Barr virus reactivation and tumor progression of nasopharyngeal carcinoma cells.

Science.gov (United States)

Fang, Chih-Yeu; Huang, Sheng-Yen; Wu, Chung-Chun; Hsu, Hui-Yu; Chou, Sheng-Ping; Tsai, Ching-Hwa; Chang, Yao; Takada, Kenzo; Chen, Jen-Yang

2012-01-01

Seroepidemiological studies imply a correlation between Epstein-Barr virus (EBV) reactivation and the development of nasopharyngeal carcinoma (NPC). N-nitroso compounds, phorbols, and butyrates are chemicals found in food and herb samples collected from NPC high-risk areas. These chemicals have been reported to be risk factors contributing to the development of NPC, however, the underlying mechanism is not fully understood. We have demonstrated previously that low dose N-methyl-N'-nitro-N-nitrosoguanidine (MNNG, 0.1 µg/ml) had a synergistic effect with 12-O-tetradecanoylphorbol-13-acetate (TPA) and sodium butyrate (SB) in enhancing EBV reactivation and genome instability in NPC cells harboring EBV. Considering that residents in NPC high-risk areas may contact regularly with these chemical carcinogens, it is vital to elucidate the relation between chemicals and EBV and their contributions to the carcinogenesis of NPC. In this study, we constructed a cell culture model to show that genome instability, alterations of cancer hallmark gene expression, and tumorigenicity were increased after recurrent EBV reactivation in NPC cells following combined treatment of TPA/SB and MNNG. NPC cells latently infected with EBV, NA, and the corresponding EBV-negative cell, NPC-TW01, were periodically treated with MNNG, TPA/SB, or TPA/SB combined with MNNG. With chemically-induced recurrent reactivation of EBV, the degree of genome instability was significantly enhanced in NA cells treated with a combination of TPA/SB and MNNG than those treated individually. The Matrigel invasiveness, as well as the tumorigenicity in mouse, was also enhanced in NA cells after recurrent EBV reactivation. Expression profile analysis by microarray indicates that many carcinogenesis-related genes were altered after recurrent EBV reactivation, and several aberrations observed in cell lines correspond to alterations in NPC lesions. These results indicate that cooperation between chemical carcinogens can

Image-based modeling of flow and reactive transport in porous media

Science.gov (United States)

Qin, Chao-Zhong; Hoang, Tuong; Verhoosel, Clemens V.; Harald van Brummelen, E.; Wijshoff, Herman M. A.

2017-04-01

Due to the availability of powerful computational resources and high-resolution acquisition of material structures, image-based modeling has become an important tool in studying pore-scale flow and transport processes in porous media [Scheibe et al., 2015]. It is also playing an important role in the upscaling study for developing macroscale porous media models. Usually, the pore structure of a porous medium is directly discretized by the voxels obtained from visualization techniques (e.g. micro CT scanning), which can avoid the complex generation of computational mesh. However, this discretization may considerably overestimate the interfacial areas between solid walls and pore spaces. As a result, it could impact the numerical predictions of reactive transport and immiscible two-phase flow. In this work, two types of image-based models are used to study single-phase flow and reactive transport in a porous medium of sintered glass beads. One model is from a well-established voxel-based simulation tool. The other is based on the mixed isogeometric finite cell method [Hoang et al., 2016], which has been implemented in the open source Nutils (http://www.nutils.org). The finite cell method can be used in combination with isogeometric analysis to enable the higher-order discretization of problems on complex volumetric domains. A particularly interesting application of this immersed simulation technique is image-based analysis, where the geometry is smoothly approximated by segmentation of a B-spline level set approximation of scan data [Verhoosel et al., 2015]. Through a number of case studies by the two models, we will show the advantages and disadvantages of each model in modeling single-phase flow and reactive transport in porous media. Particularly, we will highlight the importance of preserving high-resolution interfaces between solid walls and pore spaces in image-based modeling of porous media. References Hoang, T., C. V. Verhoosel, F. Auricchio, E. H. van

Real rock-microfluidic flow cell: A test bed for real-time in situ analysis of flow, transport, and reaction in a subsurface reactive transport environment.

Science.gov (United States)

Singh, Rajveer; Sivaguru, Mayandi; Fried, Glenn A; Fouke, Bruce W; Sanford, Robert A; Carrera, Martin; Werth, Charles J

2017-09-01

Physical, chemical, and biological interactions between groundwater and sedimentary rock directly control the fundamental subsurface properties such as porosity, permeability, and flow. This is true for a variety of subsurface scenarios, ranging from shallow groundwater aquifers to deeply buried hydrocarbon reservoirs. Microfluidic flow cells are now commonly being used to study these processes at the pore scale in simplified pore structures meant to mimic subsurface reservoirs. However, these micromodels are typically fabricated from glass, silicon, or polydimethylsiloxane (PDMS), and are therefore incapable of replicating the geochemical reactivity and complex three-dimensional pore networks present in subsurface lithologies. To address these limitations, we developed a new microfluidic experimental test bed, herein called the Real Rock-Microfluidic Flow Cell (RR-MFC). A porous 500μm-thick real rock sample of the Clair Group sandstone from a subsurface hydrocarbon reservoir of the North Sea was prepared and mounted inside a PDMS microfluidic channel, creating a dynamic flow-through experimental platform for real-time tracking of subsurface reactive transport. Transmitted and reflected microscopy, cathodoluminescence microscopy, Raman spectroscopy, and confocal laser microscopy techniques were used to (1) determine the mineralogy, geochemistry, and pore networks within the sandstone inserted in the RR-MFC, (2) analyze non-reactive tracer breakthrough in two- and (depth-limited) three-dimensions, and (3) characterize multiphase flow. The RR-MFC is the first microfluidic experimental platform that allows direct visualization of flow and transport in the pore space of a real subsurface reservoir rock sample, and holds potential to advance our understandings of reactive transport and other subsurface processes relevant to pollutant transport and cleanup in groundwater, as well as energy recovery. Copyright © 2017 Elsevier B.V. All rights reserved.

Hot gas flow cell for optical measurements on reactive gases

DEFF Research Database (Denmark)

Grosch, Helge; Fateev, Alexander; Nielsen, Karsten Lindorff

2013-01-01

A new design is presented for a gas flow cell for reactive gases at high temperatures. The design features three heated sections that are separated by flow windows. This design avoids the contact of reactive gases with the material of the exchangeable optical windows. A gas cell with this design ......-resolution measurements are presented for the absorption cross-section of sulfur dioxide (SO2) in the UV range up to 773 K (500 degrees C)...

Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu [Nagoya University, Department of Mechanical Science and Engineering, Nagoya (Japan); Kubo, Takashi [Meijo University, Faculty of Science and Technology, Nagoya (Japan)

2012-11-15

This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction (A+B{yields}R), streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions. (orig.)

The surface chemical reactivity of particles and its impact on human health

Science.gov (United States)

Setyan, A.; Sauvain, J. J.; Riediker, M.; Guillemin, M.; Rossi, M. J.

2017-12-01

The chemical composition of the particle-air interface is the gateway to chemical reactions of gases with condensed phase particles. It is of prime importance to understand the reactivity of particles and their interaction with surrounding gases, biological membranes, and solid supports. We used a Knudsen flow reactor to quantify functional groups on the surface of a few selected particle types. This technique is based on a heterogeneous titration reaction between a probe gas and a specific functional group on the particle surface. Six probe gases have been selected for the identification and quantification of important functional groups: N(CH3)3 for the titration of acidic sites, NH2OH for the detection of carbonyl functions (aldehydes and ketones) and/or oxidized sites owing to its strong reducing properties, CF3COOH and HCl for basic sites of different strength, O3 and NO2 for oxidizable groups. We also studied the kinetics of the reactions between particles and probe gases (uptake coefficient γ0). We tested the surface chemical composition and oxidation states of laboratory-generated aerosols (3 amorphous carbons, 2 flame soots, 2 Diesel particles, 2 secondary organic aerosols [SOA], 4 multiwall carbon nanotubes [MWCNT], 3 TiO2, and 2 metal salts) and of aerosols sampled in several bus depots. The sampling of particles in the bus depots was accompanied by the collection of urine samples of mechanics working full-time in these bus depots, and the quantification of 8-hydroxy-2'-deoxyguanosine, a biomarker of oxidative stress. The increase in oxidative stress biomarker levels over a working day was correlated (pcellular antioxidants.

Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

Energy Technology Data Exchange (ETDEWEB)

Malek, Ali; Balawender, Robert, E-mail: rbalawender@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, PL-01-224 Warsaw (Poland)

2015-02-07

The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor.

Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

International Nuclear Information System (INIS)

Malek, Ali; Balawender, Robert

2015-01-01

The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor

Core 2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

Energy Technology Data Exchange (ETDEWEB)

Samper, J.; Juncosa, R.; Delgado, J.; Montenegro, L. [Universidad de A Coruna (Spain)

2000-07-01

Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

Core2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

International Nuclear Information System (INIS)

Samper, J.; Juncosa, R.; Delgado, J.; Montenegro, L.

2000-01-01

Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

Core 2D. A code for non-isothermal water flow and reactive solute transport. Users manual version 2

Energy Technology Data Exchange (ETDEWEB)

Samper, J; Juncosa, R; Delgado, J; Montenegro, L [Universidad de A Coruna (Spain)

2000-07-01

Understanding natural groundwater quality patterns, quantifying groundwater pollution and assessing the effects of waste disposal, require modeling tools accounting for water flow, and transport of heat and dissolved species as well as their complex interactions with solid and gases phases. This report contains the users manual of CORE ''2D Version V.2.0, a COde for modeling water flow (saturated and unsaturated), heat transport and multicomponent Reactive solute transport under both local chemical equilibrium and kinetic conditions. it is an updated and improved version of CORE-LE-2D V0 (Samper et al., 1988) which in turns is an extended version of TRANQUI, a previous reactive transport code (ENRESA, 1995). All these codes were developed within the context of Research Projects funded by ENRESA and the European Commission. (Author)

Fluxes of chemically reactive species inferred from mean concentration measurements

NARCIS (Netherlands)

Galmarini, S.; Vilà-Guerau De Arellano, J.; Duyzer, J.H.

1997-01-01

A method is presented for the calculation of the fluxes of chemically reactive species on the basis of routine measurements of meteorological variables and chemical species. The method takes explicity into account the influence of chemical reactions on the fluxes of the species. As a demonstration

Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition

Science.gov (United States)

2017-09-30

Report: Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer ...Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition Report Term: 0-Other Email: pcappillino... Layer Electroless Deposition (ALED, Figure 1) is the ability to tune growth mechanism, hence growth morphology, by altering conditions. In this

Using laboratory flow experiments and reactive chemical transport modeling for designing waterflooding of the Agua Fria Reservoir, Poza Rica-Altamira Field, Mexico

Energy Technology Data Exchange (ETDEWEB)

Birkle, P.; Pruess, K.; Xu, T.; Figueroa, R.A. Hernandez; Lopez, M. Diaz; Lopez, E. Contreras

2008-10-01

Waterflooding for enhanced oil recovery requires that injected waters must be chemically compatible with connate reservoir waters, in order to avoid mineral dissolution-and-precipitation cycles that could seriously degrade formation permeability and injectivity. Formation plugging is a concern especially in reservoirs with a large content of carbonates, such as calcite and dolomite, as such minerals typically react rapidly with an aqueous phase, and have strongly temperature-dependent solubility. Clay swelling can also pose problems. During a preliminary waterflooding pilot project, the Poza Rica-Altamira oil field, bordering the Gulf coast in the eastern part of Mexico, experienced injectivity loss after five months of reinjection of formation waters into well AF-847 in 1999. Acidizing with HCl restored injectivity. We report on laboratory experiments and reactive chemistry modeling studies that were undertaken in preparation for long-term waterflooding at Agua Frma. Using analogous core plugs obtained from the same reservoir interval, laboratory coreflood experiments were conducted to examine sensitivity of mineral dissolution and precipitation effects to water composition. Native reservoir water, chemically altered waters, and distilled water were used, and temporal changes in core permeability, mineral abundances and aqueous concentrations of solutes were monitored. The experiments were simulated with the multi-phase, nonisothermal reactive transport code TOUGHREACT, and reasonable to good agreement was obtained for changes in solute concentrations. Clay swelling caused an additional impact on permeability behavior during coreflood experiments, whereas the modeled permeability depends exclusively on chemical processes. TOUGHREACT was then used for reservoir-scale simulation of injecting ambient-temperature water (30 C, 86 F) into a reservoir with initial temperature of 80 C (176 F). Untreated native reservoir water was found to cause serious porosity and

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

Science.gov (United States)

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-06-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

Light Water Breeder Reactor (LWBR) flow coefficient of reactivity: (LWBR Development Program)

International Nuclear Information System (INIS)

Sarber, W.K.; Stout, J.W.; Atherton, R.

1987-06-01

This report discusses the results of an experimental program to measure and categorize the causes for increases in the magnitude of the LWBR flow coefficient of reactivity at 10,932 EFPH from previously measured near zero values to a value of about 6 x 10 -4 Δ rho for a flow decrease from 100 to 80% of full flow. Reactor protection analyses confirmed that existing protection systems were adequate for continued operation. Subsequently, the flow coefficient decreased in magnitude to approximately 2.25 x 10 -4 Δ rho at 20,000 EFPH and remained about constant through the remainder of core life, 29,047 EFPH. The increase in flow coefficient of reactivity is attributed to a flow-force dependent change in the effective core diameter such that an increase in core flow decreased the core diameter, resulting in an increase in fuel-to-water ratio and a consequent decrease in the reactivity of this relatively undermoderated core. This report discusses why the increased flow coefficient did not occur until after 10,932 EFPH and why the magnitude of flow coefficient reduced with continued core operation

An iterative method for controlling reactive power flow in boundary transformers

Energy Technology Data Exchange (ETDEWEB)

Trigo, Angel L.; Martinez, Jose L.; Riquelme, Jesus; Romero, Esther [Department of Electrical Engineering, University of Seville (Spain)

2011-02-15

This paper presents an operational tool designed to help the system operator to control the reactive power flow in transmission-subtransmission boundary transformers. The main objective is to determine the minimum number of control actions necessary to ensure that reactive power flows in transmission/subtransmission transformers remain within limits. The proposed iterative procedure combines the use of a linear programming problem and a load flow tool. The linear programming assumes a linear behaviour between dependent and control variables around an operating point, modelled with sensitivities. Experimental results regarding IEEE systems are provided comparing the performance of the proposed approach with that of a conventional optimal power flow. (author)

Chemical stability and in chemico reactivity of 24 fragrance ingredients of concern for skin sensitization risk assessment.

Science.gov (United States)

Avonto, Cristina; Wang, Mei; Chittiboyina, Amar G; Vukmanovic, Stanislav; Khan, Ikhlas A

2018-02-01

Twenty-four pure fragrance ingredients have been identified as potential concern for skin sensitization. Several of these compounds are chemically unstable and convert into reactive species upon exposure to air or light. In the present work, a systematic investigation of the correlation between chemical stability and reactivity has been undertaken. The compounds were subjected to forced photodegradation for three months and the chemical changes were studied with GC-MS. At the end of the stability study, two-thirds of the samples were found to be unstable. The generation of chemically reactive species was investigated using the in chemico HTS-DCYA assay. Eleven and fourteen compounds were chemically reactive before and after three months, respectively. A significant increase in reactivity upon degradation was found for isoeugenol, linalool, limonene, lyral, citronellol and geraniol; in the same conditions, the reactivity of hydroxycitronellal decreased. The non-reactive compounds α-isomethyl ionone, benzyl alcohol, amyl cinnamal and farnesol became reactive after photo-oxidative degradation. Overall, forced degradation resulted in four non-reactive fragrance compounds to display in chemico thiol reactivity, while ten out of 24 compounds remained inactive. Chemical degradation does not necessarily occur with generation of reactive species. Non-chemical activation may be involved for the 10 stable unreactive compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

TOUGHREACT Version 2.0: A simulator for subsurface reactive transport under non-isothermal multiphase flow conditions

Energy Technology Data Exchange (ETDEWEB)

Xu, T.; Spycher, N.; Sonnenthal, E.; Zhang, G.; Zheng, L.; Pruess, K.

2010-08-01

TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media, and was developed by introducing reactive chemistry into the multiphase fluid and heat flow simulator TOUGH2 V2. The first version of TOUGHREACT was released to the public through the U.S. Department of Energy's Energy Science and Technology Software Center (ESTSC) in August 2004. It is among the most frequently requested of ESTSC's codes. The code has been widely used for studies in CO{sub 2} geological sequestration, nuclear waste isolation, geothermal energy development, environmental remediation, and increasingly for petroleum applications. Over the past several years, many new capabilities have been developed, which were incorporated into Version 2 of TOUGHREACT. Major additions and improvements in Version 2 are discussed here, and two application examples are presented: (1) long-term fate of injected CO{sub 2} in a storage reservoir and (2) biogeochemical cycling of metals in mining-impacted lake sediments.

Application of Newton's optimal power flow in voltage/reactive power control

Energy Technology Data Exchange (ETDEWEB)

Bjelogrlic, M.; Babic, B.S. (Electric Power Board of Serbia, Belgrade (YU)); Calovic, M.S. (Dept. of Electrical Engineering, University of Belgrade, Belgrade (YU)); Ristanovic, P. (Institute Nikola Tesla, Belgrade (YU))

1990-11-01

This paper considers an application of Newton's optimal power flow to the solution of the secondary voltage/reactive power control in transmission networks. An efficient computer program based on the latest achievements in the sparse matrix/vector techniques has been developed for this purpose. It is characterized by good robustness, accuracy and speed. A combined objective function appropriate for various system load levels with suitable constraints, for treatment of the power system security and economy is also proposed. For the real-time voltage/reactive power control, a suboptimal power flow procedure has been derived by using the reduced set of control variables. This procedure is based on the sensitivity theory applied to the determination of zones for the secondary voltage/reactive power control and corresponding reduced set of regulating sources, whose reactive outputs represent control variables in the optimal power flow program. As a result, the optimal power flow program output becomes a schedule to be used by operators in the process of the real-time voltage/reactive power control in both normal and emergency operating states.

Modeling of flow and reactive transport in IPARS

KAUST Repository

Wheeler, Mary Fanett

2012-03-11

In this work, we describe a number of efficient and locally conservative methods for subsurface flow and reactive transport that have been or are currently being implemented in the IPARS (Integrated Parallel and Accurate Reservoir Simulator). For flow problems, we consider discontinuous Galerkin (DG) methods and mortar mixed finite element methods. For transport problems, we employ discontinuous Galerkin methods and Godunov-mixed methods. For efficient treatment of reactive transport simulations, we present a number of state-of-the-art dynamic mesh adaptation strategies and implementations. Operator splitting approaches and iterative coupling techniques are also discussed. Finally, numerical examples are provided to illustrate the capability of IPARS to treat general biogeochemistry as well as the effectivity of mesh adaptations with DG for transport. © 2012 Bentham Science Publishers. All rights reserved.

On the thermal stability for a model reactive flow with viscous dissipation

International Nuclear Information System (INIS)

Okoya, S.S.

2006-12-01

We study the thermal stability of a reactive flow of a third-grade fluid with viscous heating and chemical reaction between two horizontal flat plates, where the top is moving with a uniform speed and the bottom plate is fixed in the presence of an imposed pressure gradient. This study is a natural continuation of earlier work on rectilinear shear flows. The governing equations are non-dimensionalized and the resulting system of equations are not coupled. An approximate explicit solution is found for the flow velocity using homotopy - perturbation technique and the range of validity is determined. After the velocity is known, the heat transport may be analyzed. It is found that the temperature solution depends on the non-Newtonian material parameter of the fluid, Λ, viscous heating parameter, Γ, and an exponent, m. Attention is focused upon the disappearance of criticality of the solution set {β, δ, θ max } for various values of Λ, Γ and m, and the numerical computations are presented graphically to show salient features of the solution set. (author)

Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

Science.gov (United States)

Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

2014-09-01

A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

Modeling of flow and reactive transport in IPARS

KAUST Repository

Wheeler, Mary Fanett; Sun, Shuyu; Thomas, Sunil G.

2012-01-01

In this work, we describe a number of efficient and locally conservative methods for subsurface flow and reactive transport that have been or are currently being implemented in the IPARS (Integrated Parallel and Accurate Reservoir Simulator

Reactive flow analysis with fluorine thermal dissociation in a FLUOREX flame reactor

International Nuclear Information System (INIS)

Ohtsuka, Masaya; Tagawa, Hisato; Sasahira, Akira; Hoshino, Kuniyoshi; Kawamura, Fumio; Homma, Shunji; Amano, Osamu

2004-01-01

A reactive flow analysis method for flame reactors of the FLUOREX (Hybrid Process of Fluoride Volatility and Solvent Extraction) method was been developed. Transport equations for UO 2 /PuO 2 mixed particles were formulated in the Lagrangian framework and several fluid/particles interactions were modeled using mass, momentum and energy exchanges through surface chemical reactions, forces and heat transfers. The coal combustion model was modified without devolatilization and the char burnout model was replaced by the UO 2 /PuO 2 fluorination model. Overall reaction rates were calculated using the combined model of the surface reaction rate and the diffusion rate of F2 and F. Fluid flows were modeled through incompressible flows using the k-ε turbulent model in the Euler framework. A cylindrical flame reactor (φ 80 mm x 500mm was analyzed where 99%UO 2 +1%PuO 2 mixed particles were injected with Ar and 5% excess F 2 flow. The average particle diameter was 4 μm and the flow rate was 300 g/h. The fluorination reaction of PuO 2 was limited through fluorine molecular reaction but was accelerated due to fluorine thermal dissociation. The simulated corresponded to the experimental result in that both UO 2 and PuO 2 were almost completely fluorinated. (author)

Localized reactive flow in carbonate rocks: Core-flood experiments and network simulations

Science.gov (United States)

Wang, Haoyue; Bernabé, Yves; Mok, Ulrich; Evans, Brian

2016-11-01

We conducted four core-flood experiments on samples of a micritic, reef limestone from Abu Dhabi under conditions of constant flow rate. The pore fluid was water in equilibrium with CO2, which, because of its lowered pH, is chemically reactive with the limestone. Flow rates were between 0.03 and 0.1 mL/min. The difference between up and downstream pore pressures dropped to final values ≪1 MPa over periods of 3-18 h. Scanning electron microscope and microtomography imaging of the starting material showed that the limestone is mostly calcite and lacks connected macroporosity and that the prevailing pores are few microns large. During each experiment, a wormhole formed by localized dissolution, an observation consistent with the decreases in pressure head between the up and downstream reservoirs. Moreover, we numerically modeled the changes in permeability during the experiments. We devised a network approach that separated the pore space into competing subnetworks of pipes. Thus, the problem was framed as a competition of flow of the reactive fluid among the adversary subnetworks. The precondition for localization within certain time is that the leading subnetwork rapidly becomes more transmissible than its competitors. This novel model successfully simulated features of the shape of the wormhole as it grew from few to about 100 µm, matched the pressure history patterns, and yielded the correct order of magnitude of the breakthrough time. Finally, we systematically studied the impact of changing the statistical parameters of the subnetworks. Larger mean radius and spatial correlation of the leading subnetwork led to faster localization.

Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

Science.gov (United States)

Hamers, Robert J.; Wang, Yajun; Shan, Jun

1996-11-01

We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

Energy Technology Data Exchange (ETDEWEB)

Pignatelli, Rossella, E-mail: rossellapignatelli@gmail.com [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Lombardi Ingegneria S.r.l., Via Giotto 36, 20145 Milano (Italy); Comi, Claudia, E-mail: comi@stru.polimi.it [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

2013-11-15

To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

Chemical Reactivity as Described by Quantum Chemical Methods

Directory of Open Access Journals (Sweden)

F. De Proft

2002-04-01

Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

User's Guide of TOUGH2-EGS. A Coupled Geomechanical and Reactive Geochemical Simulator for Fluid and Heat Flow in Enhanced Geothermal Systems Version 1.0

Energy Technology Data Exchange (ETDEWEB)

Fakcharoenphol, Perapon [Colorado School of Mines, Golden, CO (United States); Xiong, Yi [Colorado School of Mines, Golden, CO (United States); Hu, Litang [Colorado School of Mines, Golden, CO (United States); Winterfeld, Philip H. [Colorado School of Mines, Golden, CO (United States); Xu, Tianfu [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Wu, Yu-Shu [Colorado School of Mines, Golden, CO (United States)

2013-05-01

TOUGH2-EGS is a numerical simulation program coupling geomechanics and chemical reactions for fluid and heat flows in porous media and fractured reservoirs of enhanced geothermal systems. The simulator includes the fully-coupled geomechanical (THM) module, the fully-coupled geochemical (THC) module, and the sequentially coupled reactive geochemistry (THMC) module. The fully-coupled flow-geomechanics model is developed from the linear elastic theory for the thermo-poro-elastic system and is formulated with the mean normal stress as well as pore pressure and temperature. The chemical reaction is sequentially coupled after solution of flow equations, which provides the flow velocity and phase saturation for the solute transport calculation at each time step. In addition, reservoir rock properties, such as porosity and permeability, are subjected to change due to rock deformation and chemical reactions. The relationships between rock properties and geomechanical and chemical effects from poro-elasticity theories and empirical correlations are incorporated into the simulator. This report provides the user with detailed information on both mathematical models and instructions for using TOUGH2-EGS for THM, THC or THMC simulations. The mathematical models include the fluid and heat flow equations, geomechanical equation, reactive geochemistry equations, and discretization methods. Although TOUGH2-EGS has the capability for simulating fluid and heat flows coupled with both geomechanical and chemical effects, it is up to the users to select the specific coupling process, such as THM, THC, or THMC in a simulation. There are several example problems illustrating the applications of this program. These example problems are described in details and their input data are presented. The results demonstrate that this program can be used for field-scale geothermal reservoir simulation with fluid and heat flow, geomechanical effect, and chemical reaction in porous and fractured media.

Identifying the causes of differences in ozone production from the CB05 and CBMIV chemical mechanisms

Directory of Open Access Journals (Sweden)

R. D. Saylor

2012-02-01

Full Text Available An investigation was conducted to identify the mechanistic differences between two versions of the carbon bond gas-phase chemical mechanism (CB05 and CBMIV which consistently lead to larger ground-level ozone concentrations being produced in the CB05 version of the National Air Quality Forecasting Capability (NAQFC modeling system even though the two parallel forecast systems utilize the same meteorology and base emissions and similar initial and boundary conditions. Box models of each of the mechanisms as they are implemented in the NAQFC were created and a set of 12 sensitivity simulations was designed. The sensitivity simulations independently probed the conceptual mechanistic differences between CB05 and CBMIV and were exercised over a 45-scenario simulation suite designed to emulate the wide range of chemical regimes encountered in a continental-scale atmospheric chemistry model. Results of the sensitivity simulations indicate that two sets of reactions that were included in the CB05 mechanism, but which were absent from the CBMIV mechanism, are the primary causes of the greater ozone production in the CB05 version of the NAQFC. One set of reactions recycles the higher organic peroxide species of CB05 (ROOH, resulting in additional photochemically reactive products that act to produce additional ozone in some chemical regimes. The other set of reactions recycles reactive nitrogen from less reactive forms back to NO₂, increasing the effective NO_x concentration of the system. In particular, the organic nitrate species (NTR, which was a terminal product for reactive nitrogen in the CBMIV mechanism, acts as a reservoir species in CB05 to redistribute NO_x from major source areas to potentially NO_x-sensitive areas where additional ozone may be produced in areas remote from direct NO_x sources.

To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

Science.gov (United States)

Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad

2015-08-25

Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with

Flows and chemical reactions in heterogeneous mixtures

CERN Document Server

Prud'homme, Roger

2014-01-01

This book - a sequel of previous publications 'Flows and Chemical Reactions' and 'Chemical Reactions in Flows and Homogeneous Mixtures' - is devoted to flows with chemical reactions in heterogeneous environments.  Heterogeneous media in this volume include interfaces and lines. They may be the site of radiation. Each type of flow is the subject of a chapter in this volume. We consider first, in Chapter 1, the question of the generation of environments biphasic individuals: dusty gas, mist, bubble flow.  Chapter 2 is devoted to the study at the mesoscopic scale: particle-fluid exchange of mom

Pressure sensitivity of flow oscillations in postocclusive reactive skin hyperemia.

Science.gov (United States)

Strucl, M; Peterec, D; Finderle, Z; Maver, J

1994-05-01

Skin blood flow was monitored using a laser-Doppler (LD) flowmeter in 21 healthy volunteers after an occlusion of the digital arteries. The peripheral vascular bed was exposed to occlusion ischemia of varying duration (1, 4, or 8 min) and to a change in digital arterial pressure produced by different positions of the arm above heart level to characterize the pattern of LD flow oscillations in postocclusive reactive hyperemia (PRH) and to elucidate the relevance of metabolic and myogenic mechanisms in governing its fundamental frequency. The descending part of the hyperemic flow was characterized by the appearance of conspicuous periodic oscillations with a mean fundamental frequency of 7.2 +/- 1.5 cycles/min (SD, n = 9), as assessed by a Fourier transform frequency analysis of 50-s sections of flow. The mean respiratory frequency during the periods of flow frequency analysis was 17.0 +/- 2.2 (SD, n = 9), and the PRH oscillations remained during apnea in all tested subjects. The area under the maximum flow curve increased significantly with prolongation of the occlusion (paired t test, P blood pressure in the digital arteries, which suggests the predominant role of a metabolic component in this part of the PRH response. In contrast, the fundamental frequency of PRH oscillations exhibited a significant decrease with a reduction in the estimated digital arterial pressure (linear regression, b = 0.08, P < 0.001; n = 12), but did not change with the prolongation of arterial occlusion despite a significant increase in mean LD flow (paired t test, P < 0.001; n = 9).(ABSTRACT TRUNCATED AT 250 WORDS)

Improved Reactive Flow Modeling of the LX-17 Double Shock Experiments

Science.gov (United States)

Rehagen, Thomas J.; Vitello, Peter

2017-06-01

Over driven double shock experiments provide a measurement of the properties of the reaction product states of the insensitive high explosive LX-17 (92.5% TATB and 7.5% Kel-F by weight). These experiments used two flyer materials mounted on the end of a projectile to send an initial shock through the LX-17, followed by a second shock of a higher magnitude into the detonation products. In the experiments, the explosive was initially driven by the flyer plate to pressures above the Chapman-Jouguet state. The particle velocity history was recorded by Photonic Doppler Velocimetry (PDV) probes pointing at an aluminum foil coated LiF window. The PDV data shows a sharp initial shock and decay, followed by a rounded second shock. Here, the experimental results are compared to 2D and 3D Cheetah reactive flow modeling. Our default Cheetah reactive flow model fails to accurately reproduce the decay of the first shock or the curvature or strength of the second shock. A new model is proposed in which the carbon condensate produced in the reaction zone is controlled by a kinetic rate. This allows the carbon condensate to be initially out of chemical equilibrium with the product gas. This new model reproduces the initial detonation peak and decay, and matches the curvature of the second shock, however, it still over-predicts the strength of the second shock. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344.

Reactive solute transport in physically and chemically heterogeneous porous media with multimodal reactive mineral facies: the Lagrangian approach.

Science.gov (United States)

Soltanian, Mohamad Reza; Ritzi, Robert W; Dai, Zhenxue; Huang, Chao Cheng

2015-03-01

Physical and chemical heterogeneities have a large impact on reactive transport in porous media. Examples of heterogeneous attributes affecting reactive mass transport are the hydraulic conductivity (K), and the equilibrium sorption distribution coefficient (Kd). This paper uses the Deng et al. (2013) conceptual model for multimodal reactive mineral facies and a Lagrangian-based stochastic theory in order to analyze the reactive solute dispersion in three-dimensional anisotropic heterogeneous porous media with hierarchical organization of reactive minerals. An example based on real field data is used to illustrate the time evolution trends of reactive solute dispersion. The results show that the correlation between the hydraulic conductivity and the equilibrium sorption distribution coefficient does have a significant effect on reactive solute dispersion. The anisotropy ratio does not have a significant effect on reactive solute dispersion. Furthermore, through a sensitivity analysis we investigate the impact of changing the mean, variance, and integral scale of K and Kd on reactive solute dispersion. Copyright © 2014 Elsevier Ltd. All rights reserved.

Theoretical considerations of Flow Injection Analysis in the Absence of Chemical Reactions

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov

2000-01-01

The fundamental mechanism of flow injection analysis (FIA) is assumed to be simple dissusion and the response of the detector is included in a model description that provide information about the shape of the FIA peak in terms of, basically, five parameters. Two of the five parameters are associa...... that any deviation from the features of the present model and the results of a tentative chemical reaction with one of the test compounds, is related to chemical kinetics.......The fundamental mechanism of flow injection analysis (FIA) is assumed to be simple dissusion and the response of the detector is included in a model description that provide information about the shape of the FIA peak in terms of, basically, five parameters. Two of the five parameters...

Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory.

Science.gov (United States)

Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

2017-05-31

In this work we establish a new temperature dependent procedure within the grand canonical ensemble, to avoid the Dirac delta function exhibited by some of the second order chemical reactivity descriptors based on density functional theory, at a temperature of 0 K. Through the definition of a local chemical potential designed to integrate to the global temperature dependent electronic chemical potential, the local chemical hardness is expressed in terms of the derivative of this local chemical potential with respect to the average number of electrons. For the three-ground-states ensemble model, this local hardness contains a term that is equal to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba, which integrates to the global hardness given by the difference in the first ionization potential, I, and the electron affinity, A, at any temperature. However, in the present approach one finds an additional temperature-dependent term that introduces changes at the local level and integrates to zero. Additionally, a τ-hard dual descriptor and a τ-soft dual descriptor given in terms of the product of the global hardness and the global softness multiplied by the dual descriptor, respectively, are derived. Since all these reactivity indices are given by expressions composed of terms that correspond to products of the global properties multiplied by the electrophilic or nucleophilic Fukui functions, they may be useful for studying and comparing equivalent sites in different chemical environments.

Local Chemical Reactivity of a Metal Alloy Surface

DEFF Research Database (Denmark)

Hammer, Bjørk; Scheffler, Matthias

1995-01-01

The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

Applying flow chemistry: methods, materials, and multistep synthesis.

Science.gov (United States)

McQuade, D Tyler; Seeberger, Peter H

2013-07-05

The synthesis of complex molecules requires control over both chemical reactivity and reaction conditions. While reactivity drives the majority of chemical discovery, advances in reaction condition control have accelerated method development/discovery. Recent tools include automated synthesizers and flow reactors. In this Synopsis, we describe how flow reactors have enabled chemical advances in our groups in the areas of single-stage reactions, materials synthesis, and multistep reactions. In each section, we detail the lessons learned and propose future directions.

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

International Nuclear Information System (INIS)

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

2008-01-01

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

An implicit multigrid algorithm for computing hypersonic, chemically reacting viscous flows

International Nuclear Information System (INIS)

Edwards, J.R.

1996-01-01

An implicit algorithm for computing viscous flows in chemical nonequilibrium is presented. Emphasis is placed on the numerical efficiency of the time integration scheme, both in terms of periteration workload and overall convergence rate. In this context, several techniques are introduced, including a stable, O(m 2 ) approximate factorization of the chemical source Jacobian and implementations of V-cycle and filtered multigrid acceleration methods. A five species-seventeen reaction air model is used to calculate hypersonic viscous flow over a cylinder at conditions corresponding to flight at 5 km/s, 60 km altitude and at 11.36 km/s, 76.42 km altitude. Inviscid calculations using an eleven-species reaction mechanism including ionization are presented for a case involving 11.37 km/s flow at an altitude of 84.6 km. Comparisons among various options for the implicit treatment of the chemical source terms and among different multilevel approaches for convergence acceleration are presented for all simulations

Multiphase Flow Dynamics 2 Mechanical Interactions

CERN Document Server

Kolev, Nikolay Ivanov

2012-01-01

Multi-phase flows are part of our natural environment such as tornadoes, typhoons, air and water pollution and volcanic activities as well as part of industrial technology such as power plants, combustion engines, propulsion systems, or chemical and biological industry. The industrial use of multi-phase systems requires analytical and numerical strategies for predicting their behavior. .In its fourth extended edition the successful monograph package “Multiphase Flow Daynmics” contains theory, methods and practical experience for describing complex transient multi-phase processes in arbitrary geometrical configurations, providing a systematic presentation of the theory and practice of numerical multi-phase fluid dynamics. In the present second volume the methods for describing the mechanical interactions in multiphase dynamics are provided. This fourth edition includes various updates, extensions, improvements and corrections.   "The literature in the field of multiphase flows is numerous. Therefore, it i...

APPLICATION OF MODIFIED POWER FLOW TRACING METHOD FOR REACTIVE POWER PRICING IN PRACTICAL UTILITY SYSTEM

Directory of Open Access Journals (Sweden)

M. SUSITHRA

2017-01-01

Full Text Available Competitive trend towards restructuring and unbundling of transmission services has resulted in the need to discover the impact of a particular generator to load. This paper initially presents the analysis of three different reactive power valuation methods namely, Modified Ybus , Virtual flow approach and modified power flow tracing to compute the reactive power output from a particular generator to particular load. Among these methods, the modified power flow electricity tracing method is identified as the best method to trace the reactive power contribution from various reactive power sources to loads, transmission line, etc. Also this proposed method breakdown the total reactive power loss in a transmission line into components to be allocated to individual loads. Secondly, based on this Method a novel allocation method for reactive power service for practical system is proposed. Hence, this method can be useful in providing additional insight into power system operation and can be used to modify existing tariffs of charging for reactive power transmission loss and reactive power transmission services. Simulation and comparison results are shown by taking WSCC 9 and IEEE 30 bus system as test system.

The influence of electrohydrodynamic flow on the distribution of chemical species in positive corona

Science.gov (United States)

Pontiga, Francisco; Yanallah, Khelifa; Bouazza, R.; Chen, Junhong

2015-09-01

A numerical simulation of positive corona discharge in air, including the effect of electrohydrodynamic (EHD) motion of the gas, has been carried out. Air flow is assumed to be confined between two parallel plates, and corona discharge is produced around a thin wire, midway between the plates. Therefore, fluid dynamics equations, including electrical forces, have been solved together with the continuity equation of each neutral species. The plasma chemical model included 24 chemical reactions and ten neutral species, in addition to electrons and positive ions. The results of the simulation have shown that the influence of EHD flow on the spatial distributions of the species is quite different depending on the species. Hence, reactive species like atomic oxygen and atomic nitrogen are confined to the vicinity of the wire, and they are weakly affected by the EHD gas motion. In contrast, nitrogen oxides and ozone are efficiently dragged outside the active region of the corona discharge by the EHD flow. This work was supported by the Spanish Government Agency ``Ministerio de Ciencia e Innovación'' under Contract No. FIS2011-25161.

Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

International Nuclear Information System (INIS)

Zhang, Xiaojuan; Wang, Bo; Zhan, Zhaolin; Huang, Feng

2013-01-01

V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC

Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiaojuan [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Wang, Bo [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); Zhan, Zhaolin [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Huang, Feng, E-mail: huangfeng@nimte.ac.cn [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China)

2013-07-01

V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC.

Chemical and physical characteristics of phosphate rock materials of varying reactivity

International Nuclear Information System (INIS)

Syers, J.K.; Currie, L.D.

1986-01-01

Several chemical and physical properties of 10 phosphate rock (PR) materials of varying reactivity were evaluated. The highest concentrations of As and Cd were noted. Because Cd and U can accumulate in biological systems, it may be necessary to direct more attention towards the likely implications of Cd and U concentrations when evaluating a PR for direct application. Three sequential extractions with 2% citric acid may be more useful for comparing the chemical solubility of PR materials, particularly for those containing appreciable CaC0 3 . The poor relationship obtained between surface area and the solubility of the PR materials suggests that surface area plays a secondary role to chemical reactivity in controlling the solubility of a PR in a chemical extractant. A Promesh plot provided an effective method for describing the particle-size characteristics of those PR materials which occurred as sands. Fundamental characteristics, such as mean particle size and uniformity, can readily be determined from a Promesh plot. (author)

Predictive model for convective flows induced by surface reactivity contrast

Science.gov (United States)

Davidson, Scott M.; Lammertink, Rob G. H.; Mani, Ali

2018-05-01

Concentration gradients in a fluid adjacent to a reactive surface due to contrast in surface reactivity generate convective flows. These flows result from contributions by electro- and diffusio-osmotic phenomena. In this study, we have analyzed reactive patterns that release and consume protons, analogous to bimetallic catalytic conversion of peroxide. Similar systems have typically been studied using either scaling analysis to predict trends or costly numerical simulation. Here, we present a simple analytical model, bridging the gap in quantitative understanding between scaling relations and simulations, to predict the induced potentials and consequent velocities in such systems without the use of any fitting parameters. Our model is tested against direct numerical solutions to the coupled Poisson, Nernst-Planck, and Stokes equations. Predicted slip velocities from the model and simulations agree to within a factor of ≈2 over a multiple order-of-magnitude change in the input parameters. Our analysis can be used to predict enhancement of mass transport and the resulting impact on overall catalytic conversion, and is also applicable to predicting the speed of catalytic nanomotors.

Simultaneous resolution of reactive radioactive decay, non-isothermal flow, and migration with application to the performance assessment for HLW repositories

International Nuclear Information System (INIS)

Juncosa, R.; Delgado, J.; Font, I.

2010-01-01

Radioactive decay is an important subject to take into account when studying the thermo-hydro-dynamic behavior of the buffer clay material used in the containment of radioactive waste. The modern concepts for the multibarrier design of a repository of high level waste in deep geologic formations consider that once canisters have failed, the buffer clay material must ensure the retention and/or delay of radionuclides within the time framework given in the assessment studies. Within the clay buffer, different chemical species are retarded/fixed according to several physicochemical processes (ion exchange, surface complexation, precipitation, matrix diffusion,..) but typical approaches do not consider the eventuality that radioactive species change their chemical nature (i.e. phase) thereby affecting their reactive behavior. The radioactive decay of an element takes place independently of the phase (aqueous, solid or gaseous) to which it belongs. This means that, in terms of radionuclide fixation, some geochemical processes will be effective scavengers (for instance mineral precipitation of crystal growth) while others will not (for instance ion exchange and/or sorption). In this contribution we present a reactive radioactive decay model of any number of chemical components including those that belong to decay series. The model, which is named FLOW-DECAY, also takes into account flow and isotopic migration and it has been applied considering a hypothetical model scenario provided by the project ENRESA 2000 and direct comparison with the results generated by the probabilistic code GoldSim. Results indicate that FLOW-DECAY may simulate the decay processes in a similar way that GoldSim, being the differences related to factors associated to code architecture. (orig.)

Optical, electrical and mechanical properties of the tantalum oxynitride thin films deposited by pulsing reactive gas sputtering

International Nuclear Information System (INIS)

Le Dreo, H.; Banakh, O.; Keppner, H.; Steinmann, P.-A.; Briand, D.; Rooij, N.F. de

2006-01-01

Thin films of tantalum oxynitride were prepared by reactive magnetron sputtering using a Ta target and N 2 and O 2 as reactive gases. The nitrogen flow was kept constant while the oxygen flow was pulsed periodically. The film composition evolves progressively from TaO 0.25 N 1.51 to TaO 2.42 N 0.25 while increasing the oxygen pulse duty cycle without any abrupt change in the elemental content. The optical transmission spectra of the films deposited on glass show a 'blue shift' of the absorption edge with increasing oxygen content. X-ray diffraction (XRD) patterns of all films exhibit broad peaks typical for nanocrystalline materials. Cross-section film morphology is rather featureless and surface topography is smooth exhibiting very small grains, in agreement with the results obtained by XRD. The optical properties of the films are very sensitive to their chemical composition. All films exhibit semiconducting behaviour with an optical band gap changing from 1.85 to 4.0 eV with increasing oxygen content. In order to evaluate the potential of the tantalum oxynitride films for microelectronic applications some Ta-O-N films were integrated in a MOS structure. The results of the capacitance-voltage measurements of the system Al//Ta-O-N//p-Si are discussed with respect to the chemical composition of the Ta-O-N films

On mechanisms of reactive metabolite formation from drugs.

Science.gov (United States)

Claesson, Alf; Spjuth, Ola

2013-04-01

Idiosyncratic adverse drug reactions (IADRs) cause a broad range of clinically severe conditions of which drug induced liver injury (DILI) in particular is one of the most frequent causes of safety-related drug withdrawals. The underlying cause is almost invariably formation of reactive metabolites (RM) which by attacking macromolecules induc eorgan injuries. Attempts are being made in the pharmaceutical industry to lower the risk of selecting unfit compounds as clinical candidates. Approaches vary but do not seem to be overly successful at the initial design/synthesis stage. We review here the most frequent categories of mechanisms for RM formation and propose that many cases of RMs encountered within early ADME screening can be foreseen by applying chemical and metabolic knowledge. We also mention a web tool, SpotRM, which can be used for efficient look-up and learning about drugs that have recognized IADRs likely caused by RM formation.

Importance of asparagine on the conformational stability and chemical reactivity of selected anti-inflammatory peptides

Energy Technology Data Exchange (ETDEWEB)

Soriano-Correa, Catalina, E-mail: csorico@comunidad.unam.mx [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz-Boca del Río, Universidad Veracruzana, C.P. 91700 Veracruz (Mexico); Campos-Fernández, Linda; Alvarado-Salazar, Andres [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), C.P. 09340 México, D.F. (Mexico)

2015-08-18

Highlights: • Asparagine plays an important role to anti-inflammatory effect of peptides. • The electron-donor substituent groups favor the formation of the hydrogen bonds, which contribute in the structural stability of peptides. • Chemical reactivity and the physicochemical features are crucial in the biological functions of peptides. - Abstract: Inflammatory response events are initiated by a complex series of molecular reactions that generate chemical intermediaries. The structure and properties of peptides and proteins are determined by the charge distribution of their side chains, which play an essential role in its electronic structure and physicochemical properties, hence on its biological functionality. The aim of this study was to analyze the effect of changing one central amino acid, such as substituting asparagine for aspartic acid, from Cys–Asn–Ser in aqueous solution, by assessing the conformational stability, physicochemical properties, chemical reactivity and their relationship with anti-inflammatory activity; employing quantum-chemical descriptors at the M06-2X/6-311+G(d,p) level. Our results suggest that asparagine plays a more critical role than aspartic acid in the structural stability, physicochemical features, and chemical reactivity of these tripeptides. Substituent groups in the side chain cause significant changes on the conformational stability and chemical reactivity, and consequently on their anti-inflammatory activity.

Analysis of the flow with phase change and chemical reaction with the particle interaction method. Report under the contract between JNC and Toshiba Corporation

International Nuclear Information System (INIS)

Shirakawa, Noriyuki; Horie, Hideki; Yamamoto, Yuichi

2001-02-01

The numerical thermohydraulic analysis of a LMFR component should involve its whole boundary in order to evaluate the effect of chemical reaction within it. Therefore, it becomes difficult mainly due to computing time to adopt microscopic approach for the chemical reaction directly. Thus, the thermohydraulic code is required to model the chemically reactive fluid dynamics with constitutive correlations. The reaction rate depends on the binary contact areas between components such as continuous liquids, droplets, solid particles, and bubbles. The contact areas change sharply according to the interface state between components. Since no experiments to study the jet flow with sodium-water chemical reaction have been done, the goal of this study is to obtain the knowledge of flow regimes and contact areas by analyzing the fluid dynamics of multi-phase and reactive components mechanistically with the particle interaction method. In this fiscal year, following works were performed: 1) Development and coding of the interfacial area model, 2) Development and coding of the phase change model, 3) Verification of the fundamental functions of the models, and 4) Literature investigation of the related experiments. (author)

Effects of intermittent theta burst stimulation on cerebral blood flow and cerebral vasomotor reactivity.

Science.gov (United States)

Pichiorri, Floriana; Vicenzini, Edoardo; Gilio, Francesca; Giacomelli, Elena; Frasca, Vittorio; Cambieri, Chiara; Ceccanti, Marco; Di Piero, Vittorio; Inghilleri, Maurizio

2012-08-01

To determine whether intermittent theta burst stimulation influences cerebral hemodynamics, we investigated changes induced by intermittent theta burst stimulation on the middle cerebral artery cerebral blood flow velocity and vasomotor reactivity to carbon dioxide (CO(2)) in healthy participants. The middle cerebral artery flow velocity and vasomotor reactivity were monitored by continuous transcranial Doppler sonography. Changes in cortical excitability were tested by transcranial magnetic stimulation. In 11 healthy participants, before and immediately after delivering intermittent theta burst stimulation, we tested cortical excitability measured by the resting motor threshold and motor evoked potential amplitude over the stimulated hemisphere and vasomotor reactivity to CO(2) bilaterally. The blood flow velocity was monitored in both middle cerebral arteries throughout the experimental session. In a separate session, we tested the effects of sham stimulation under the same experimental conditions. Whereas the resting motor threshold remained unchanged before and after stimulation, motor evoked potential amplitudes increased significantly (P = .04). During and after stimulation, middle cerebral artery blood flow velocities also remained bilaterally unchanged, whereas vasomotor reactivity to CO(2) increased bilaterally (P = .04). The sham stimulation left all variables unchanged. The expected intermittent theta burst stimulation-induced changes in cortical excitability were not accompanied by changes in cerebral blood flow velocities; however, the bilateral increased vasomotor reactivity suggests that intermittent theta burst stimulation influences the cerebral microcirculation, possibly involving subcortical structures. These findings provide useful information on hemodynamic phenomena accompanying intermittent theta burst stimulation, which should be considered in research aimed at developing this noninvasive, low-intensity stimulation technique for safe

Simulations of reactive transport and precipitation with smoothed particle hydrodynamics

Science.gov (United States)

Tartakovsky, Alexandre M.; Meakin, Paul; Scheibe, Timothy D.; Eichler West, Rogene M.

2007-03-01

A numerical model based on smoothed particle hydrodynamics (SPH) was developed for reactive transport and mineral precipitation in fractured and porous materials. Because of its Lagrangian particle nature, SPH has several advantages for modeling Navier-Stokes flow and reactive transport including: (1) in a Lagrangian framework there is no non-linear term in the momentum conservation equation, so that accurate solutions can be obtained for momentum dominated flows and; (2) complicated physical and chemical processes such as surface growth due to precipitation/dissolution and chemical reactions are easy to implement. In addition, SPH simulations explicitly conserve mass and linear momentum. The SPH solution of the diffusion equation with fixed and moving reactive solid-fluid boundaries was compared with analytical solutions, Lattice Boltzmann [Q. Kang, D. Zhang, P. Lichtner, I. Tsimpanogiannis, Lattice Boltzmann model for crystal growth from supersaturated solution, Geophysical Research Letters, 31 (2004) L21604] simulations and diffusion limited aggregation (DLA) [P. Meakin, Fractals, scaling and far from equilibrium. Cambridge University Press, Cambridge, UK, 1998] model simulations. To illustrate the capabilities of the model, coupled three-dimensional flow, reactive transport and precipitation in a fracture aperture with a complex geometry were simulated.

TOURGHREACT: A Simulation Program for Non-isothermal Multiphase Reactive Geochemical Transport in Variably Saturated Geologic Media

OpenAIRE

Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

2004-01-01

TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media. The program was written in Fortran 77 and developed by introducing reactive geochemistry into the multiphase fluid and heat flow simulator TOUGH2. A variety of subsurface thermo-physical-chemical processes are considered under a wide range of conditions of pressure, temperature, water saturation, ionic strength, and pH and Eh. Interactions between ...

Reactive Molecular Dynamics Simulations to Understand Mechanical Response of Thaumasite under Temperature and Strain Rate Effects.

Science.gov (United States)

Hajilar, Shahin; Shafei, Behrouz; Cheng, Tao; Jaramillo-Botero, Andres

2017-06-22

Understanding the structural, thermal, and mechanical properties of thaumasite is of great interest to the cement industry, mainly because it is the phase responsible for the aging and deterioration of civil infrastructures made of cementitious materials attacked by external sources of sulfate. Despite the importance, effects of temperature and strain rate on the mechanical response of thaumasite had remained unexplored prior to the current study, in which the mechanical properties of thaumasite are fully characterized using the reactive molecular dynamics (RMD) method. With employing a first-principles based reactive force field, the RMD simulations enable the description of bond dissociation and formation under realistic conditions. From the stress-strain curves of thaumasite generated in the x, y, and z directions, the tensile strength, Young's modulus, and fracture strain are determined for the three orthogonal directions. During the course of each simulation, the chemical bonds undergoing tensile deformations are monitored to reveal the bonds responsible for the mechanical strength of thaumasite. The temperature increase is found to accelerate the bond breaking rate and consequently the degradation of mechanical properties of thaumasite, while the strain rate only leads to a slight enhancement of them for the ranges considered in this study.

Evaluation of the chemical reactivity in lignin precursors using the Fukui function.

Science.gov (United States)

Martinez, Carmen; Rivera, José L; Herrera, Rafael; Rico, José L; Flores, Nelly; Rutiaga, José G; López, Pablo

2008-02-01

The hydroxycinnamyl alcohols: p-coumarol, coniferol and sinapol are considered the basic units and precursors of lignins models. In this work, the specific reactivity of these molecules was studied. We investigate their intrinsic chemical reactivity in terms of the Fukui function, applying the principle of hard and soft acids and bases (HSAB) in the framework of the density functional theory (DFT). Comparisons of their nucleophilic, electrophilic and free radical reactivity show their most probably sites to form linkages among them. It is found that the most reactive sites, for reactions involving free radicals, are the carbons at the beta-position in the p-coumarol and sinapol molecules, whilst the regions around the carbon-oxygen bond of the phenoxyl group are the most reactive in coniferol.

Strategies for measuring flows of reactive nitrogen at the landscape scale

DEFF Research Database (Denmark)

Theobald, M.R.; Akkal, N.; Bienkowski, J.

2011-01-01

Within a rural landscape there are flows of reactive nitrogen (Nr) through and between the soil, vegetation, atmosphere and hydrological systems as well as transfer as a result of agricultural activities. Measurements of these flows and transfers have generally been limited to individual media (e.......g., hydrological flows) or the interface between two media (e.g., exchange between the soil and the atmosphere). However, the study of flows of Nr at the landscape scale requires a more integrated approach that combines measurement techniques to quantify the flows from one medium to the next. This paper discusses...

A computational environment for creating and testing reduced chemical kinetic mechanisms

Energy Technology Data Exchange (ETDEWEB)

Montgomery, C.J.; Swensen, D.A.; Harding, T.V.; Cremer, M.A.; Bockelie, M.J. [Reaction Engineering International, Salt Lake City, UT (USA)

2002-02-01

This paper describes software called computer assisted reduced mechanism problem solving environment (CARM-PSE) that gives the engineer the ability to rapidly set up, run and examine large numbers of problems comparing detailed and reduced (approximate) chemistry. CARM-PSE integrates the automatic chemical mechanism reduction code CARM and the codes that simulate perfectly stirred reactors and plug flow reactors into a user-friendly computational environment. CARM-PSE gives the combustion engineer the ability to easily test chemical approximations over many hundreds of combinations of inputs in a multidimensional parameter space. The demonstration problems compare detailed and reduced chemical kinetic calculations for methane-air combustion, including nitrogen oxide formation, in a stirred reactor and selective non-catalytic reduction of NOx, in coal combustion flue gas.

Temperature dependence on sodium-water chemical reaction

International Nuclear Information System (INIS)

Tamura, Kenta; Deguchi, Yoshihiro; Suzuki, Koichi; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2012-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. A quasi one-dimensional flame model is also applied to a sodium-water counter-flow reaction field. Temperature, H 2 , H 2 O, OH, Na and Particulate matter were measured using laser induced fluorescence and CARS in the counter-flow reaction field. The temperature of the reaction field was also modified to reduce the condensation of Na in the reaction zone. (author)

The reactive metabolite target protein database (TPDB)--a web-accessible resource.

Science.gov (United States)

Hanzlik, Robert P; Koen, Yakov M; Theertham, Bhargav; Dong, Yinghua; Fang, Jianwen

2007-03-16

The toxic effects of many simple organic compounds stem from their biotransformation to chemically reactive metabolites which bind covalently to cellular proteins. To understand the mechanisms of cytotoxic responses it may be important to know which proteins become adducted and whether some may be common targets of multiple toxins. The literature of this field is widely scattered but expanding rapidly, suggesting the need for a comprehensive, searchable database of reactive metabolite target proteins. The Reactive Metabolite Target Protein Database (TPDB) is a comprehensive, curated, searchable, documented compilation of publicly available information on the protein targets of reactive metabolites of 18 well-studied chemicals and drugs of known toxicity. TPDB software enables i) string searches for author names and proteins names/synonyms, ii) more complex searches by selecting chemical compound, animal species, target tissue and protein names/synonyms from pull-down menus, and iii) commonality searches over multiple chemicals. Tabulated search results provide information, references and links to other databases. The TPDB is a unique on-line compilation of information on the covalent modification of cellular proteins by reactive metabolites of chemicals and drugs. Its comprehensiveness and searchability should facilitate the elucidation of mechanisms of reactive metabolite toxicity. The database is freely available at http://tpdb.medchem.ku.edu/tpdb.html.

Comparison of reactivity in a flow reactor and a single cylinder engine

Energy Technology Data Exchange (ETDEWEB)

Natelson, Robert H.; Johnson, Rodney O.; Kurman, Matthew S.; Cernansky, Nicholas P.; Miller, David L. [Department of Mechanical Engineering and Mechanics, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104-2875 (United States)

2010-10-15

The relative reactivity of 2:1:1 and 1:1:1 mixtures of n-decane:n-butylcyclohexane:n-butylbenzene and an average sample of JP-8 were evaluated in a single cylinder engine and compared to results obtained in a pressurized flow reactor. At compression ratios of 14:1, 15:1, and 16:1, inlet temperature of 500 K, inlet pressure of 0.1 MPa, equivalence ratio of 0.23, and engine speed of 800 RPM, the autoignition delay times were, from shortest to longest, the 2:1:1, followed by the 1:1:1, and then the JP-8. This order corresponded with recent results in a pressurized flow reactor, where the preignition oxidation chemistry was monitored at temperatures of 600-800 K, 0.8 MPa pressure, and an equivalence ratio of 0.30, and where the preignition reactivity from highest to lowest was the 2:1:1, followed by the 1:1:1, and the JP-8. This shows that the relative reactivity at low temperatures in the flow reactor tracks the autoignition tendencies in the engine for these particular fuels. (author) the computed experimental error. (author)

Phase equilibria in chemical reactive fluid mixtures

International Nuclear Information System (INIS)

Maurer, Gerd

2011-01-01

Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author's group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the 'chilled ammonia process'. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of 'counter ion condensation' and methods to model the Gibbs free energy of such solutions.

A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity

Science.gov (United States)

Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

Shock loading and reactive flow modeling studies of void induced AP/AL/HTPB propellant

Science.gov (United States)

Miller, P. J.; Lindfors, A. J.

1998-07-01

The unreactive Hugoniot of a class 1.3 propellant has been investigated by shock compression experiments. The results are analyzed in terms of an ignition and growth reactive flow model using the DYNA2D hydrocode. The calculated shock ignition parameters of the model show a linear dependence on measured void volume which appears to reproduce the observed gauge records well. Shock waves were generated by impact in a 75 mm single stage powder gun. Manganin and PVDF pressure gauges provided pressure-time histories to 140 kbar. The propellants were of similar formulation differing only in AP particle size and the addition of a burn rate modifer (Fe2O3) from that of previous investigations. Results show neglible effect of AP particle size on shock response in contrast to the addition of Fe2O3 which appears to `stiffen' the unreactive Hugoniot and enhances significantly the reactive rates under shock. The unreactive Hugoniot, within experimental error, compares favorably to the solid AP Hugoniot. Shock experiments were performed on propellant samples strained to induce insitu voids. The material state was quantified by uniaxial tension dialatometry. The experimental records show a direct correlation between void volume (0 to 1.7%) and chemical reactivity behind the shock front. These results are discussed in terms of `hot spot' ignition resulting from the shock collapse of the voids.

Dual continuum models of fully coupled non-isothermal multiphase flow and reactive transport in porous media

International Nuclear Information System (INIS)

Zheng, L.; Samper, J.

2005-01-01

Full text of publication follows: Double porosity, double permeability and dual continuum models (DCM) are widely used for modeling preferential water flow and mass transport in unsaturated and fractured media. Here we present a DCM of fully coupled non-isothermal multiphase flow and reactive transport model for the FEBEX compacted bentonite, a material which exhibits a double porosity behavior.. FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project dealing with the bentonite engineered barrier designed for sealing and containment of a high level radioactive waste repository. Our DCM considers inter-aggregate macro-pores, and intra-aggregate and interlayer micro-pores. Two types of DCMs are tested: the dual continuum connected matrix (DCCM) and the dual continuum dis connected matrix (DCDM). Liquid flow in macro-pores is described with a mass conservation equation accounting for Darcian flow, chemical and thermal osmosis. In DCCM, water flux in micropores is calculated with a modified Darcy's law by adding a chemical osmosis term. A simple mass balance equation is used for DCDM which contains a storage and a water exchange term for water in micropores. A mixed type of water exchange term is adopted which includes a second order term accounting for water transfer due to the difference in liquid pressure and a first order term accounting for the gradient in chemical osmosis pressure. Equations of mass conservation for liquid, gas and heat in macro-pores and liquid mass conservation in micropores are solved by using a Newton-Raphson method. Two transport equations with a coupling interaction term are used to describe solute transport in macro- and micro-pores. The coupling term contains a first order diffusion term and a convection term (solute exchange due to water exchange). Transport equations as well as chemical reactions in the two domains are solved by means of a sequential iteration method. All these feature have been

Effect of Anisotropy Structure on Plume Entropy and Reactive Mixing in Helical Flows

DEFF Research Database (Denmark)

Ye, Yu; Chiogna, Gabriele; Lu, Chunhui

2018-01-01

Plume dilution and reactive mixing can be considerably enhanced by helical flows occurring in three-dimensional anisotropic porous media. In this study, we perform conservative and reactive transport simulations considering different anisotropy structures of a single inclusion with the objective...... of exploring the effect of the inclusion’s geometry and orientation on the patterns of twisted streamlines and on the overall dilution and reaction of solute plumes. We analyzed 100 different scenarios by varying key parameters such as the angle of the anisotropic structures with respect to the average flow...... velocity, the spacing between alternated heterogeneous zones of coarse and fine materials, the permeability contrast between such matrices, and the magnitude of the seepage velocity. Entropy conservation equations and entropy-based metrics for both conservative and reactive species were adopted to quantify...

Effects of chewing rate and reactive hyperemia on blood flow in denture-supporting mucosa during simulated chewing.

Science.gov (United States)

Ogino, Takamichi; Ueda, Takayuki; Ogami, Koichiro; Koike, Takashi; Sakurai, Kaoru

2017-01-01

We examined how chewing rate and the extent of reactive hyperemia affect the blood flow in denture-supporting mucosa during chewing. The left palatal mucosa was loaded under conditions of simulated chewing or simulated clenching for 30s, and the blood flow during loading was recorded. We compared the relative blood flow during loading under conditions that recreated different chewing rates by combining duration of chewing cycle (DCC) and occlusal time (OT): fast chewing group, typical chewing group, slow chewing group and clenching group. The relationship between relative blood flow during simulated chewing and the extent of reactive hyperemia was also analyzed. When comparing the different chewing rate, the relative blood flow was highest in fast chewing rate, followed by typical chewing rate and slow chewing rate. Accordingly, we suggest that fast chewing increases the blood flow more than typical chewing or slow chewing. There was a significant correlation between the amount of blood flow during simulated chewing and the extent of reactive hyperemia. Within the limitations of this study, we concluded that slow chewing induced less blood flow than typical or fast chewing in denture-supporting mucosa and that people with less reactive hyperemia had less blood flow in denture-supporting mucosa during chewing. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

Science.gov (United States)

Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

2016-12-01

In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ( 1 H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Chemical Identity of Interaction of Protein with Reactive Metabolite of Diosbulbin B In Vitro and In Vivo

Directory of Open Access Journals (Sweden)

Kai Wang

2017-08-01

Full Text Available Diosbulbin B (DIOB, a hepatotoxic furan-containing compound, is a primary ingredient in Dioscorea bulbifera L., a common herbal medicine. Metabolic activation is required for DIOB-induced liver injury. Protein covalent binding of an electrophilic reactive intermediate of DIOB is considered to be one of the key mechanisms of cytotoxicity. A bromine-based analytical technique was developed to characterize the chemical identity of interaction of protein with reactive intermediate of DIOB. Cysteine (Cys and lysine (Lys residues were found to react with the reactive intermediate to form three types of protein modification, including Cys adduction, Schiff’s base, and Cys/Lys crosslink. The crosslink showed time- and dose-dependence in animals given DIOB. Ketoconazole pretreatment decreased the formation of the crosslink derived from DIOB, whereas pretreatment with dexamethasone or buthionine sulfoximine increased such protein modification. These data revealed that the levels of hepatic protein adductions were proportional to the severity of hepatotoxicity of DIOB.

Chemical reactivity of analogous technetium(V) and rhenium(V) dioxo complexes

International Nuclear Information System (INIS)

Kremer, C.; Kremer, E.; Leon, A.

1993-01-01

All complexes of the series [MO 2 L 2 ] + (M = Tc, Re, L = ethylenediamine (en), 1,3-diaminopropane (1,3-dap)) have been synthesized and their chemical reactivities investigated. The following properties were studied: stability of the aqueous solutions at different pH values, substitution kinetics, lipophilicity and protein binding. The complexes show very similar reactivity in aqueous solution. From a radiopharmaceutical point of view, no significant difference in their in vivo behavior is expected. (author) 12 refs.; 1 fig.; 3 tabs

Chemical mechanical polishing characteristics of ITO thin film prepared by RF magnetron sputtering

International Nuclear Information System (INIS)

Lee, Kang-Yeon; Choi, Gwon-Woo; Kim, Yong-Jae; Choi, Youn-Ok; Kim, Nam-Oh

2012-01-01

Indium-tin-oxide (ITO) thin films have attracted intensive interest because of their unique properties of good conductivity, high optical transmittance over the visible region and easy patterning ability. ITO thin films have found many applications in anti-static coatings, thermal heaters, solar cells, flat panel displays (FPDs), liquid crystal displays (LCDs), electroluminescent devices, sensors and organic light-emitting diodes (OLEDs). ITO thin films are generally fabricated by using various methods, such as spraying, chemical vapor deposition (CVD), evaporation, electron gun deposition, direct current electroplating, high frequency sputtering, and reactive sputtering. In this research, ITO films were grown on glass substrates by using a radio-frequency (RF) magnetron sputtering method. In order to achieve a high transmittance and a low resistivity, we examined the various film deposition conditions, such as substrate temperature, working pressure, annealing temperature, and deposition time. Next, in order to improve the surface quality of the ITO thin films, we performed a chemical mechanical polishing (CMP) with different process parameters and compared the electrical and the optical properties of the polished ITO thin films. The best CMP conditions with a high removal rate, low nonuniformity, low resistivity and high transmittance were as follows: platen speed, head speed, polishing time, and slurry flow rate of 30 rpm, 30 rpm, 60 sec, and 60 ml/min, respectively.

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

Science.gov (United States)

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

Working principle and structure characteristics analysis of the reactivity control drive mechanism

International Nuclear Information System (INIS)

Zhao Tianyu; Huang Zhiyong; Chen Feng; He Xuedong

2010-01-01

The startup, power regulation and safety shutdown of the nuclear reactor are operated by the reactivity control devices. Reactivity control drive mechanism is a key mechanical transmission component, which directly control the location of the neutron absorber in the core. Its working condition is complex, and its service life should be long., which requires high reliability. PWR as well as newly developed different type of reactors have different control devices drive mechanism. This paper mainly do analysis and comparison about the working environment, mechanical transmission principle, structure, performance, service life and other aspects of PWR, HTR control devices drive mechanism. In addition, this paper is also based on the working principles of reactive control devices drive mechanism, also consider the trends of its design and test verification by the international countries, and discussed the method and feasibility of improving and perfecting the structure and function of drive mechanism. (authors)

Neural mechanisms of reactivation-induced updating that enhance and distort memory

OpenAIRE

St. Jacques, Peggy L.; Olm, Christopher; Schacter, Daniel L.

2013-01-01

We remember a considerable number of personal experiences because we are frequently reminded of them, a process known as memory reactivation. Although memory reactivation helps to stabilize and update memories, reactivation may also introduce distortions if novel information becomes incorporated with memory. Here we used functional magnetic resonance imaging (fMRI) to investigate the neural mechanisms mediating reactivation-induced updating in memory for events experienced during a museum tou...

Enhancing the design of in situ chemical barriers with multicomponent reactive transport modeling

International Nuclear Information System (INIS)

Sevougian, S.D.; Steefel, C.I.; Yabusaki, S.B.

1994-11-01

This paper addresses the need for systematic control of field-scale performance in the emplacement and operation of in situ chemical treatment barriers; in particular, it addresses the issue of how the local coupling of reaction kinetics and material heterogeneities at the laboratory or bench scale can be accurately upscaled to the field. The authors have recently developed modeling analysis tools that can explicitly account for all relevant chemical reactions that accompany the transport of reagents and contaminants through a chemically and physically heterogeneous subsurface rock or soil matrix. These tools are incorporated into an enhanced design methodology for in situ chemical treatment technologies, and the new methodology is demonstrated in the ongoing design of a field experiment for the In Situ Redox Manipulation (ISRM) project at the U.S. Department of Energy (DOE) Hanford Site. The ISRM design approach, which systematically integrates bench-scale and site characterization information, provides an ideal test for the new reactive transport techniques. The need for the enhanced chemistry capability is demonstrated by an example that shows how intra-aqueous redox kinetics can affect the transport of reactive solutes. Simulations are carried out on massively parallel computer architectures to resolve the influence of multiscale heterogeneities on multicomponent, multidimensional reactive transport. The technology will soon be available to design larger-scale remediation schemes

PFLOTRAN: Reactive Flow & Transport Code for Use on Laptops to Leadership-Class Supercomputers

Energy Technology Data Exchange (ETDEWEB)

Hammond, Glenn E.; Lichtner, Peter C.; Lu, Chuan; Mills, Richard T.

2012-04-18

PFLOTRAN, a next-generation reactive flow and transport code for modeling subsurface processes, has been designed from the ground up to run efficiently on machines ranging from leadership-class supercomputers to laptops. Based on an object-oriented design, the code is easily extensible to incorporate additional processes. It can interface seamlessly with Fortran 9X, C and C++ codes. Domain decomposition parallelism is employed, with the PETSc parallel framework used to manage parallel solvers, data structures and communication. Features of the code include a modular input file, implementation of high-performance I/O using parallel HDF5, ability to perform multiple realization simulations with multiple processors per realization in a seamless manner, and multiple modes for multiphase flow and multicomponent geochemical transport. Chemical reactions currently implemented in the code include homogeneous aqueous complexing reactions and heterogeneous mineral precipitation/dissolution, ion exchange, surface complexation and a multirate kinetic sorption model. PFLOTRAN has demonstrated petascale performance using 2{sup 17} processor cores with over 2 billion degrees of freedom. Accomplishments achieved to date include applications to the Hanford 300 Area and modeling CO{sub 2} sequestration in deep geologic formations.

Self-organised synthesis of Rh nanostructures with tunable chemical reactivity

Directory of Open Access Journals (Sweden)

Lizzit S

2007-01-01

Full Text Available AbstractNonequilibrium periodic nanostructures such as nanoscale ripples, mounds and rhomboidal pyramids formed on Rh(110 are particularly interesting as candidate model systems with enhanced catalytic reactivity, since they are endowed with steep facets running along nonequilibrium low-symmetry directions, exposing a high density of undercoordinated atoms. In this review we report on the formation of these novel nanostructured surfaces, a kinetic process which can be controlled by changing parameters such as temperature, sputtering ion flux and energy. The role of surface morphology with respect to chemical reactivity is investigated by analysing the carbon monoxide dissociation probability on the different nanostructured surfaces.

An efficient unstructured WENO method for supersonic reactive flows

Science.gov (United States)

Zhao, Wen-Geng; Zheng, Hong-Wei; Liu, Feng-Jun; Shi, Xiao-Tian; Gao, Jun; Hu, Ning; Lv, Meng; Chen, Si-Cong; Zhao, Hong-Da

2018-03-01

An efficient high-order numerical method for supersonic reactive flows is proposed in this article. The reactive source term and convection term are solved separately by splitting scheme. In the reaction step, an adaptive time-step method is presented, which can improve the efficiency greatly. In the convection step, a third-order accurate weighted essentially non-oscillatory (WENO) method is adopted to reconstruct the solution in the unstructured grids. Numerical results show that our new method can capture the correct propagation speed of the detonation wave exactly even in coarse grids, while high order accuracy can be achieved in the smooth region. In addition, the proposed adaptive splitting method can reduce the computational cost greatly compared with the traditional splitting method.

Coupled Flow and Mechanics in Porous and Fractured Media*

Science.gov (United States)

Martinez, M. J.; Newell, P.; Bishop, J.

2012-12-01

Numerical models describing subsurface flow through deformable porous materials are important for understanding and enabling energy security and climate security. Some applications of current interest come from such diverse areas as geologic sequestration of anthropogenic CO2, hydro-fracturing for stimulation of hydrocarbon reservoirs, and modeling electrochemistry-induced swelling of fluid-filled porous electrodes. Induced stress fields in any of these applications can lead to structural failure and fracture. The ultimate goal of this research is to model evolving faults and fracture networks and flow within the networks while coupling to flow and mechanics within the intact porous structure. We report here on a new computational capability for coupling of multiphase porous flow with geomechanics including assessment of over-pressure-induced structural damage. The geomechanics is coupled to the flow via the variation in the fluid pore pressures, whereas the flow problem is coupled to mechanics by the concomitant material strains which alter the pore volume (porosity field) and hence the permeability field. For linear elastic solid mechanics a monolithic coupling strategy is utilized. For nonlinear elastic/plastic and fractured media, a segregated coupling is presented. To facilitate coupling with disparate flow and mechanics time scales, the coupling strategy allows for different time steps in the flow solve compared to the mechanics solve. If time steps are synchronized, the controller allows user-specified intra-time-step iterations. The iterative coupling is dynamically controlled based on a norm measuring the degree of variation in the deformed porosity. The model is applied for evaluation of the integrity of jointed caprock systems during CO2 sequestration operations. Creation or reactivation of joints can lead to enhanced pathways for leakage. Similarly, over-pressures can induce flow along faults. Fluid flow rates in fractures are strongly dependent on the

Neural mechanisms of reactivation-induced updating that enhance and distort memory.

Science.gov (United States)

St Jacques, Peggy L; Olm, Christopher; Schacter, Daniel L

2013-12-03

We remember a considerable number of personal experiences because we are frequently reminded of them, a process known as memory reactivation. Although memory reactivation helps to stabilize and update memories, reactivation may also introduce distortions if novel information becomes incorporated with memory. Here we used functional magnetic resonance imaging (fMRI) to investigate the neural mechanisms mediating reactivation-induced updating in memory for events experienced during a museum tour. During scanning, participants were shown target photographs to reactivate memories from the museum tour followed by a novel lure photograph from an alternate tour. Later, participants were presented with target and lure photographs and asked to determine whether the photographs showed a stop they visited during the tour. We used a subsequent memory analysis to examine neural recruitment during reactivation that was associated with later true and false memories. We predicted that the quality of reactivation, as determined by online ratings of subjective recollection, would increase subsequent true memories but also facilitate incorporation of the lure photograph, thereby increasing subsequent false memories. The fMRI results revealed that the quality of reactivation modulated subsequent true and false memories via recruitment of left posterior parahippocampal, bilateral retrosplenial, and bilateral posterior inferior parietal cortices. However, the timing of neural recruitment and the way in which memories were reactivated contributed to differences in whether memory reactivation led to distortions or not. These data reveal the neural mechanisms recruited during memory reactivation that modify how memories will be subsequently retrieved, supporting the flexible and dynamic aspects of memory.

Two Experiments to Approach the Boltzmann Factor: Chemical Reaction and Viscous Flow

Science.gov (United States)

Fazio, Claudio; Battaglia, Onofrio R.; Guastella, Ivan

2012-01-01

In this paper we discuss a pedagogical approach aimed at pointing out the role played by the Boltzmann factor in describing phenomena usually perceived as regulated by different mechanisms of functioning. Experimental results regarding some aspects of a chemical reaction and of the viscous flow of some liquids are analysed and described in terms…

Dynamics of Reactive Microbial Hotspots in Concentration Gradient.

Science.gov (United States)

Hubert, A.; Farasin, J.; Tabuteau, H.; Dufresne, A.; Meheust, Y.; Le Borgne, T.

2017-12-01

In subsurface environments, bacteria play a major role in controlling the kinetics of a broad range of biogeochemical reactions. In such environments, nutrients fluxes and solute concentrations needed for bacteria metabolism may be highly variable in space and intermittent in time. This can lead to the formation of reactive hotspots where and when conditions are favorable to particular microorganisms, hence inducing biogeochemical reaction kinetics that differ significantly from those measured in homogeneous model environments. To investigate the impact of chemical gradients on the spatial structure and temporal dynamics of subsurface microorganism populations, we develop microfluidic cells allowing for a precise control of flow and chemical gradient conditions, as well as quantitative monitoring of the bacteria's spatial distribution and biofilm development. Using the non-motile Escherichia coli JW1908-1 strain and Gallionella capsiferriformans ES-2 as model organisms, we investigate the behavior and development of bacteria over a range of single and double concentration gradients in the concentrations of nutrients, electron donors and electron acceptors. We measure bacterial activity and population growth locally in precisely known hydrodynamic and chemical environments. This approach allows time-resolved monitoring of the location and intensity of reactive hotspots in micromodels as a function of the flow and chemical gradient conditions. We compare reactive microbial hotspot dynamics in our micromodels to classic growth laws and well-known growth parameters for the laboratory model bacteria Escherichia coli.We also discuss consequences for the formation and temporal dynamics of biofilms in the subsurface.

Unravelling chemical priming machinery in plants: the role of reactive oxygen-nitrogen-sulfur species in abiotic stress tolerance enhancement.

Science.gov (United States)

Antoniou, Chrystalla; Savvides, Andreas; Christou, Anastasis; Fotopoulos, Vasileios

2016-10-01

Abiotic stresses severely limit crop yield and their detrimental effects are aggravated by climate change. Chemical priming is an emerging field in crop stress management. The exogenous application of specific chemical agents before stress events results in tolerance enhancement and reduction of stress impacts on plant physiology and growth. However, the molecular mechanisms underlying the remarkable effects of chemical priming on plant physiology remain to be elucidated. Reactive oxygen, nitrogen and sulfur species (RONSS) are molecules playing a vital role in the stress acclimation of plants. When applied as priming agents, RONSS improve stress tolerance. This review summarizes the recent knowledge on the role of RONSS in cell signalling and gene regulation contributing to abiotic stress tolerance enhancement. Copyright © 2016 Elsevier Ltd. All rights reserved.

Power and power-to-flow reactivity transfer functions in EBR-II [Experimental Breeder Reactor II] fuel

International Nuclear Information System (INIS)

Grimm, K.N.; Meneghetti, D.

1989-01-01

Reactivity transfer functions are important in determining the reactivity history during a power transient. Overall nodal transfer functions have been calculated for different subassembly types in the Experimental Breeder Reactor II (EBR-II). Steady-state calculations for temperature changes and, hence, reactivities for power changes have been separated into power and power-to-flow-dependent terms. Axial nodal transfer functions separated into power and power-to-flow-dependent components are reported in this paper for a typical EBR-II fuel pin. This provides an improved understanding of the time dependence of these components in transient situations

The reactive metabolite target protein database (TPDB – a web-accessible resource

Directory of Open Access Journals (Sweden)

Dong Yinghua

2007-03-01

Full Text Available Abstract Background The toxic effects of many simple organic compounds stem from their biotransformation to chemically reactive metabolites which bind covalently to cellular proteins. To understand the mechanisms of cytotoxic responses it may be important to know which proteins become adducted and whether some may be common targets of multiple toxins. The literature of this field is widely scattered but expanding rapidly, suggesting the need for a comprehensive, searchable database of reactive metabolite target proteins. Description The Reactive Metabolite Target Protein Database (TPDB is a comprehensive, curated, searchable, documented compilation of publicly available information on the protein targets of reactive metabolites of 18 well-studied chemicals and drugs of known toxicity. TPDB software enables i string searches for author names and proteins names/synonyms, ii more complex searches by selecting chemical compound, animal species, target tissue and protein names/synonyms from pull-down menus, and iii commonality searches over multiple chemicals. Tabulated search results provide information, references and links to other databases. Conclusion The TPDB is a unique on-line compilation of information on the covalent modification of cellular proteins by reactive metabolites of chemicals and drugs. Its comprehensiveness and searchability should facilitate the elucidation of mechanisms of reactive metabolite toxicity. The database is freely available at http://tpdb.medchem.ku.edu/tpdb.html

Mapping Global Flows of Chemicals: From Fossil Fuel Feedstocks to Chemical Products.

Science.gov (United States)

Levi, Peter G; Cullen, Jonathan M

2018-02-20

Chemical products are ubiquitous in modern society. The chemical sector is the largest industrial energy consumer and the third largest industrial emitter of carbon dioxide. The current portfolio of mitigation options for the chemical sector emphasizes upstream "supply side" solutions, whereas downstream mitigation options, such as material efficiency, are given comparatively short shrift. Key reasons for this are the scarcity of data on the sector's material flows, and the highly intertwined nature of its complex supply chains. We provide the most up to date, comprehensive and transparent data set available publicly, on virgin production routes in the chemical sector: from fossil fuel feedstocks to chemical products. We map global mass flows for the year 2013 through a complex network of transformation processes, and by taking account of secondary reactants and by-products, we maintain a full mass balance throughout. The resulting data set partially addresses the dearth of publicly available information on the chemical sector's supply chain, and can be used to prioritise downstream mitigation options.

Chemical and biological activity in open flows: A dynamical system approach

International Nuclear Information System (INIS)

Tel, Tamas; Moura, Alessandro de; Grebogi, Celso; Karolyi, Gyoergy

2005-01-01

Chemical and biological processes often take place in fluid flows. Many of them, like environmental or microfluidical ones, generate filamentary patterns which have a fractal structure, due to the presence of chaos in the underlying advection dynamics. In such cases, hydrodynamical stirring strongly couples to the reactivity of the advected species: the outcome of the reaction is then typically different from that of the same reaction taking place in a well-mixed environment. Here we review recent progress in this field, which became possible due to the application of methods taken from dynamical system theory. We place special emphasis on the derivation of effective rate equations which contain singular terms expressing the fact that the reaction takes place on a moving fractal catalyst, on the unstable foliation of the reaction free advection dynamics

Framework for reactive mass transport

DEFF Research Database (Denmark)

Jensen, Mads Mønster; Johannesson, Björn; Geiker, Mette Rica

2014-01-01

Reactive transport modeling is applicable for a range of porous materials. Here the modeling framework is focused on cement-based materials, where ion diffusion and migration are described by the Poisson-Nernst-Planck equation system. A two phase vapor/liquid flow model, with a sorption hysteresis...... description is coupled to the system. The mass transport is solved by using the finite element method where the chemical equilibrium is solved explicitly by an operator splitting method. The IPHREEQC library is used as chemical equilibrium solver. The equation system, solved by IPHREEQC, is explained...

Reactive flow modeling of small scale detonation failure experiments for a baseline non-ideal explosive

Energy Technology Data Exchange (ETDEWEB)

Kittell, David E.; Cummock, Nick R.; Son, Steven F. [School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907 (United States)

2016-08-14

Small scale characterization experiments using only 1–5 g of a baseline ammonium nitrate plus fuel oil (ANFO) explosive are discussed and simulated using an ignition and growth reactive flow model. There exists a strong need for the small scale characterization of non-ideal explosives in order to adequately survey the wide parameter space in sample composition, density, and microstructure of these materials. However, it is largely unknown in the scientific community whether any useful or meaningful result may be obtained from detonation failure, and whether a minimum sample size or level of confinement exists for the experiments. In this work, it is shown that the parameters of an ignition and growth rate law may be calibrated using the small scale data, which is obtained from a 35 GHz microwave interferometer. Calibration is feasible when the samples are heavily confined and overdriven; this conclusion is supported with detailed simulation output, including pressure and reaction contours inside the ANFO samples. The resulting shock wave velocity is most likely a combined chemical-mechanical response, and simulations of these experiments require an accurate unreacted equation of state (EOS) in addition to the calibrated reaction rate. Other experiments are proposed to gain further insight into the detonation failure data, as well as to help discriminate between the role of the EOS and reaction rate in predicting the measured outcome.

Deposition of chemically reactive and repellent sites on biosensor chips for reduced non-specific binding.

Science.gov (United States)

Gandhiraman, R P; Gubala, V; Le, N C H; Nam, Le Cao Hoai; Volcke, C; Doyle, C; James, B; Daniels, S; Williams, D E

2010-08-01

The performances of new polymeric materials with excellent optical properties and good machinability have led the biomedical diagnostics industry to develop cheap disposable biosensor platforms appropriate for point of care applications. Zeonor, a type of cycloolefin polymer (COP), is one such polymer that presents an excellent platform for biosensor chips. These polymer substrates have to be modified to have suitable physico-chemical properties for immobilizing proteins. In this work, we have demonstrated the amine functionalization of COP substrates, by plasma enhanced chemical vapour deposition (PECVD), through codeposition of ethylene diamine and 3-aminopropyltriethoxysilane precursors, for building chemistries on the plastic chip. The elemental composition, adhesion, ageing and reactivity of the plasma polymerized film were examined. The Si-O functionality present in amino silane contributed for a good interfacial adhesion of the coating to COP substrates and also acted as a network building layer for plasma polymerization. Wet chemical modification was then carried out on the amine functionalized chips to create chemically reactive isothiocyanate sites and protein repellent fluorinated sites on the same chip. The density of the reactive and repellent sites was altered by choosing appropriate mixtures of homofunctional phenyldiisothiocyanate (PDITC), pentafluoroisothiocyanate (5FITC) and phenylisothiocyanate (PITC) compounds. By tailoring the density of reactive binding sites and protein repellent sites, the non-specific binding of ssDNA has been decreased to a significant extent. Copyright 2010 Elsevier B.V. All rights reserved.

Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Sibener, Steven J. [Univ. of Chicago, IL (United States). James Franck Inst. and Dept. of Chemistry

2014-03-11

This research program explored the efficacy of using molecular-level manipulation, imaging and scanning tunneling spectroscopy in conjunction with supersonic molecular beam gas-surface scattering to significantly enhance our understanding of chemical processes occurring on well-characterized interfaces. One program focus was on the spatially-resolved emergent behavior of complex reaction systems as a function of the local geometry and density of adsorbate-substrate systems under reaction conditions. Another focus was on elucidating the emergent electronic and related reactivity characteristics of intentionally constructed single and multicomponent atom- and nanoparticle-based materials. We also examined emergent chirality and self-organization in adsorbed molecular systems where collective interactions between adsorbates and the supporting interface lead to spatial symmetry breaking. In many of these studies we combined the advantages of scanning tunneling (STM) and atomic force (AFM) imaging, scanning tunneling local electronic spectroscopy (STS), and reactive supersonic molecular beams to elucidate precise details of interfacial reactivity that had not been observed by more traditional surface science methods. Using these methods, it was possible to examine, for example, the differential reactivity of molecules adsorbed at different bonding sites in conjunction with how reactivity is modified by the local configuration of nearby adsorbates. At the core of this effort was the goal of significantly extending our understanding of interfacial atomic-scale interactions to create, with intent, molecular assemblies and materials with advanced chemical and physical properties. This ambitious program addressed several key topics in DOE Grand Challenge Science, including emergent chemical and physical properties in condensed phase systems, novel uses of chemical imaging, and the development of advanced reactivity concepts in combustion and catalysis including carbon

Chemical reactivity of cation-exchanged zeolites

NARCIS (Netherlands)

Pidko, E.A.

2008-01-01

Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

Effect of various nitrogen flow ratios on the optical properties of (Hf:N-DLC films prepared by reactive magnetron sputtering

Directory of Open Access Journals (Sweden)

Meng Qi

2017-08-01

Full Text Available Hf and N co-doped diamond-like carbon [(Hf:N-DLC] films were deposited on 316L stainless steel and glass substrates through reactive magnetron sputtering of hafnium and carbon targets at various nitrogen flow ratios (R=N2/[N2+CH4+Ar]. The effects of chemical composition and crystal structure on the optical properties of the (Hf:N-DLC films were studied. The obtained films consist of uniform HfN nanocrystallines embedded into the DLC matrix. The size of the graphite clusters with sp2 bonds (La and the ID/IG ratio increase to 2.47 nm and 3.37, respectively, with increasing R. The optical band gap of the films decreases from 2.01 eV to 1.84 eV with increasing R. This finding is consistent with the trends of structural transformations and could be related to the increase in the density of π-bonds due to nitrogen incorporation. This paper reports the influence of nitrogen flow ratio on the correlation among the chemical composition, crystal structure, and optical properties of (Hf:N-DLC films.

Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

NARCIS (Netherlands)

Scheeren, H.A.

2003-01-01

The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large

Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

Directory of Open Access Journals (Sweden)

J. Rinne

2012-06-01

Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

Mechanics of occurrence of critical flow in compressible two-phase flow

International Nuclear Information System (INIS)

Katto, Yoshiro; Sudo, Yukio

1976-01-01

Fundamental framework of mechanics for the occurrence of critical flow is investigated, following the principle that the critical flow appears as a limit in a continuous change of state of flow along a nozzle (or a pipe) and should be derived only from simultaneous mechanical equations concerned with the flow. Mathematical procedures with which the critical flow: (i) the single phase flow of an arbitrary fluid, unrestricted by the equation of state of ideal gas, where the number of simultaneous equations is equal to the number of independent variables, and (ii) the one-component, separated two-phase flow under saturated condition, where the number of equations exceeds that of variables. In each case, interesting mechanism of leading to the occurrence of a limiting state of flow at a definite cross-section in a nozzle (incl. a pipe) is clarified, and a definite state of flow at the critical cross-section is also determined. Then, the analysis is extended to the critical flow which should appear in the completely isolated and the homogeneously dispersed, two-component, two-phase flow (composed of a compressible and an incompressible substance). It is found that the analyses of these special flow patterns provide several supplementary information to the mechanics of critical flow. (auth.)

Nano-patterning of perpendicular magnetic recording media by low-energy implantation of chemically reactive ions

International Nuclear Information System (INIS)

Martin-Gonzalez, M.S.; Briones, F.; Garcia-Martin, J.M.; Montserrat, J.; Vila, L.; Faini, G.; Testa, A.M.; Fiorani, D.; Rohrmann, H.

2010-01-01

Magnetic nano-patterning of perpendicular hard disk media with perpendicular anisotropy, but preserving disk surface planarity, is presented here. Reactive ion implantation is used to locally modify the chemical composition (hence the magnetization and magnetic anisotropy) of the Co/Pd multilayer in irradiated areas. The procedure involves low energy, chemically reactive ion irradiation through a resist mask. Among N, P and As ions, P are shown to be most adequate to obtain optimum bit density and topography flatness for industrial Co/Pd multilayer media. The effect of this ion contributes to isolate perpendicular bits by destroying both anisotropy and magnetic exchange in the irradiated areas. Low ion fluences are effective due to the stabilization of atomic displacement levels by the chemical effect of covalent impurities.

Reactive chemically modified piezoelectric crystal detectors: A new class of high-selectivity sensors

International Nuclear Information System (INIS)

Fadeev, A.Yu.; Filatov, A.L.; Lisichkin, G.V.

1994-01-01

A great number of works have focused on the study of properties of modified piezoelectric quartz crystal detectors (PQCDs) coated with sorbing substrates and on applying sensors based on them for the analysis of diluted gas mixtures and solutions. This work offers a new class of gravemetric sensors characterized by a reversible chemical reaction that occurs on their surface. Silica films are proposed as a sorbing coating of quartz detectors, and a chemical modification of a surface is suggested for covalent fixation of the necessary compounds. PQCDs were chemically modified with reactive diene derivatives that can also act as dienophiles. Hexachlorocyclopentadiene (HCCPD, resonater I) and cyclopentadiene (CPD, resonator II) were fixed on a PQCD surface in several stages. After treatment with the resonaters, the PQCD in a CPD gas phase exhibited time dependent frequency shifts from 20-100 Hz. The results suggest that there is a reversible chemical reaction on the electrode surface of resonators I and II when they interact with CPD vapors. Therefore, PQCDs modified with reactive dienes were prepared for the first time and may be employed as selective sensors for CPD

Modification of the finite element heat and mass transfer code (FEHMN) to model multicomponent reactive transport

International Nuclear Information System (INIS)

Viswanathan, H.S.

1995-01-01

The finite element code FEHMN is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developed hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent K d model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect 14 C transport at Yucca Mountain. The simulations also provide that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies

Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials

Science.gov (United States)

2016-06-01

2013 4. TITLE AND SUBTITLE Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials 5a...directions for future decontamination formulation approaches. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent... DECONTAMINANTS TO PROVIDE HAZARD MITIGATION OF CHEMICAL WARFARE AGENTS FROM MATERIALS 1. INTRODUCTION Decontamination of materials is the

Simulation of reactive polydisperse sprays strongly coupled to unsteady flows in solid rocket motors: Efficient strategy using Eulerian Multi-Fluid methods

Science.gov (United States)

Sibra, A.; Dupays, J.; Murrone, A.; Laurent, F.; Massot, M.

2017-06-01

In this paper, we tackle the issue of the accurate simulation of evaporating and reactive polydisperse sprays strongly coupled to unsteady gaseous flows. In solid propulsion, aluminum particles are included in the propellant to improve the global performances but the distributed combustion of these droplets in the chamber is suspected to be a driving mechanism of hydrodynamic and acoustic instabilities. The faithful prediction of two-phase interactions is a determining step for future solid rocket motor optimization. When looking at saving computational ressources as required for industrial applications, performing reliable simulations of two-phase flow instabilities appears as a challenge for both modeling and scientific computing. The size polydispersity, which conditions the droplet dynamics, is a key parameter that has to be accounted for. For moderately dense sprays, a kinetic approach based on a statistical point of view is particularly appropriate. The spray is described by a number density function and its evolution follows a Williams-Boltzmann transport equation. To solve it, we use Eulerian Multi-Fluid methods, based on a continuous discretization of the size phase space into sections, which offer an accurate treatment of the polydispersion. The objective of this paper is threefold: first to derive a new Two Size Moment Multi-Fluid model that is able to tackle evaporating polydisperse sprays at low cost while accurately describing the main driving mechanisms, second to develop a dedicated evaporation scheme to treat simultaneously mass, moment and energy exchanges with the gas and between the sections. Finally, to design a time splitting operator strategy respecting both reactive two-phase flow physics and cost/accuracy ratio required for industrial computations. Using a research code, we provide 0D validations of the new scheme before assessing the splitting technique's ability on a reference two-phase flow acoustic case. Implemented in the industrial

Tangential stretching rate (TSR) analysis of non premixed reactive flows

KAUST Repository

Valorani, Mauro

2016-10-16

We discuss how the Tangential stretching rate (TSR) analysis, originally developed and tested for spatially homogeneous systems (batch reactors), is extended to spatially non homogeneous systems. To illustrate the effectiveness of the TSR diagnostics, we study the ignition transient in a non premixed, reaction–diffusion model in the mixture fraction space, whose dependent variables are temperature and mixture composition. The reactive mixture considered is syngas/air. A detailed H2/CO mechanism with 12 species and 33 chemical reactions is employed. We will discuss two cases, one involving only kinetics as a model of front propagation purely driven by spontaneous ignition, the other as a model of deflagration wave involving kinetics/diffusion coupling. We explore different aspects of the system dynamics such as the relative role of diffusion and kinetics, the evolution of kinetic eigenvalues, and of the tangential stretching rates computed by accounting for the combined action of diffusion and kinetics as well for kinetics only. We propose criteria based on the TSR concept which allow to identify the most ignitable conditions and to discriminate between spontaneous ignition and deflagration front.

Acceleration methods for multi-physics compressible flow

Science.gov (United States)

Peles, Oren; Turkel, Eli

2018-04-01

In this work we investigate the Runge-Kutta (RK)/Implicit smoother scheme as a convergence accelerator for complex multi-physics flow problems including turbulent, reactive and also two-phase flows. The flows considered are subsonic, transonic and supersonic flows in complex geometries, and also can be either steady or unsteady flows. All of these problems are considered to be a very stiff. We then introduce an acceleration method for the compressible Navier-Stokes equations. We start with the multigrid method for pure subsonic flow, including reactive flows. We then add the Rossow-Swanson-Turkel RK/Implicit smoother that enables performing all these complex flow simulations with a reasonable CFL number. We next discuss the RK/Implicit smoother for time dependent problem and also for low Mach numbers. The preconditioner includes an intrinsic low Mach number treatment inside the smoother operator. We also develop a modified Roe scheme with a corresponding flux Jacobian matrix. We then give the extension of the method for real gas and reactive flow. Reactive flows are governed by a system of inhomogeneous Navier-Stokes equations with very stiff source terms. The extension of the RK/Implicit smoother requires an approximation of the source term Jacobian. The properties of the Jacobian are very important for the stability of the method. We discuss what the chemical physics theory of chemical kinetics tells about the mathematical properties of the Jacobian matrix. We focus on the implication of the Le-Chatelier's principle on the sign of the diagonal entries of the Jacobian. We present the implementation of the method for turbulent flow. We use a two RANS turbulent model - one equation model - Spalart-Allmaras and a two-equation model - k-ω SST model. The last extension is for two-phase flows with a gas as a main phase and Eulerian representation of a dispersed particles phase (EDP). We present some examples for such flow computations inside a ballistic evaluation

Modeling Chemically Reactive Flow of Sutterby Nanofluid by a Rotating Disk in Presence of Heat Generation/Absorption

Science.gov (United States)

Hayat, T.; Ahmad, Salman; Ijaz Khan, M.; Alsaedi, A.

2018-05-01

In this article we investigate the flow of Sutterby liquid due to rotating stretchable disk. Mass and heat transport are analyzed through Brownian diffusion and thermophoresis. Further the effects of magnetic field, chemical reaction and heat source are also accounted. We employ transformation procedure to obtain a system of nonlinear ODE’s. This system is numerically solved by Built-in-Shooting method. Impacts of different involved parameter on velocity, temperature and concentration are described. Velocity, concentration and temperature gradients are numerically computed. Obtained results show that velocity is reduced through material parameter. Temperature and concentration are enhanced with thermophoresis parameter.

Cross-coupling effects in chemically non-equilibrium viscous compressible flows

International Nuclear Information System (INIS)

Kustova, E.V.; Giordano, D.

2011-01-01

Graphical abstract: Self-cosistent kinetic-theory description of chemical-reaction rates and mean normal stress in one-temperature viscous compressible gas flows. Reaearch highlights: → In chemically non-equilibrium viscous compressible flows, the rate of each reaction depends on the velocity divergence and rates of all other reactions. → Cross effects between the rates of chemical reactions and normal mean stress can be found in the symmetric form and expressed in terms of the reaction affinities. → In the case of small affinities, the entropy production is unconditionally non-negative; in the case of finite affinities, the entropy production related to the scalar forces has no definite sign. - Abstract: A closed self-consistent description of a one-temperature non-equilibrium reacting flow is presented on the basis of the kinetic theory methods. A general case including internal degrees of freedom, dissociation-recombination and exchange reactions, and arbitrary values of affinities of chemical reactions is considered. Chemical-reaction rates and mean normal stress in viscous compressible flows are studied and a symmetric cross coupling between these terms is found. It is shown that the rate of each chemical reaction and the mean normal stress depend on velocity divergence and affinities of all chemical reactions; the law of mass action is violated in viscous flows. The results obtained in the frame of linear irreversible thermodynamics can be deduced from the proposed model for the particular case of small affinities. The reciprocal Onsager-Casimir relations are verified, the symmetry of kinetic coefficients is demonstrated, and the entropy production in a viscous flow is studied.

Chemical Modeling of the Reactivity of Short-Lived Greenhouse Gases: A Model Inter-Comparison Prescribing a Well-Measured, Remote Troposphere

Science.gov (United States)

Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

2018-01-01

We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating over the data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14,880 parcels along 180W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10% of parcels control 25-30% of the total reactivities), but do not fully agree on which parcels comprise the top 10%. Distinct differences in specific features occur, including the regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the 6 models tested here, 3 are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify 4, effectively distinct, chemical models. Based on this work, we suggest that water vapor differences in

Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

Science.gov (United States)

Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R

2006-04-15

The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

Algorithm For Hypersonic Flow In Chemical Equilibrium

Science.gov (United States)

Palmer, Grant

1989-01-01

Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

Calculating Shocks In Flows At Chemical Equilibrium

Science.gov (United States)

Eberhardt, Scott; Palmer, Grant

1988-01-01

Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

GEOCHEMISTRY OF SUBSURFACE REACTIVE BARRIERS FOR REMEDIATION OF CONTAMINATED GROUND WATER

Science.gov (United States)

Reactive barriers that couple subsurface fluid flow with a passive chemical treatment zone are emerging, cost effective approaches for in-situ remediation of contaminated groundwater. Factors such as the build-up of surface precipitates, bio-fouling, and changes in subsurface tr...

Mechanics of fluid flow

CERN Document Server

Basniev, Kaplan S; Chilingar, George V 0

2012-01-01

The mechanics of fluid flow is a fundamental engineering discipline explaining both natural phenomena and human-induced processes, and a thorough understanding of it is central to the operations of the oil and gas industry.  This book, written by some of the world's best-known and respected petroleum engineers, covers the concepts, theories, and applications of the mechanics of fluid flow for the veteran engineer working in the field and the student, alike.  It is a must-have for any engineer working in the oil and gas industry.

Reactivity of polychlorinated biphenyls in nucleophilic and electrophilic substitutions

Energy Technology Data Exchange (ETDEWEB)

Gorbunova, Tatyana I., E-mail: gorbunova@ios.uran.ru [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation); Subbotina, Julia O. [Ural Federal University named after the first President of Russia B.N. Yeltsin, Mira St., 19, Ekaterinburg 620002 (Russian Federation); Saloutin, Viktor I.; Chupakhin, Oleg N. [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation)

2014-08-15

Graphical abstract: - Highlights: • Quantum chemical calculations were carried out for PCBs congeners. • Calculated descriptors were used to explain the PCBs reactivity in S{sub N} and S{sub E} substitutions. • Obtained data were used to estimate the PCBs reactivity in the S{sub N} reactions. • Calculated descriptors were insufficient to explain the PCBs reactivity in the S{sub E} reactions. • New neutralization methods of the large-capacity PCBs were discussed. - Abstract: To explain the chemical reactivity of polychlorinated biphenyls in nucleophilic (S{sub N}) and electrophilic (S{sub E}) substitutions, quantum chemical calculations were carried out at the B3LYP/6-31G(d) level of the Density Functional Theory in gas phase. Carbon atomic charges in biphenyl structure were calculated by the Atoms-in-Molecules method. Chemical hardness and global electrophilicity index parameters were determined for congeners. A comparison of calculated descriptors and experimental data for congener reactivity in the S{sub N} and S{sub E} reactions was made. It is shown that interactions in the S{sub N} mechanism are reactions of the hard acid–hard base type, these are the most effective in case of highly chlorinated substrates. To explain the congener reactivity in the S{sub E} reactions, correct descriptors were not established. The obtained results can be used to carry out chemical transformations of the polychlorinated biphenyls in order to prepare them for microbiological destruction or preservation.

Feasibility Study for the Use of Green, Bio-Based, Efficient Reactive Sorbent Material to Neutralize Chemical Warfare Agents

Science.gov (United States)

2012-08-02

REPORT Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents 14. ABSTRACT 16...way cellulose, lignin and hemicelluloses interact as well as whole wood dissolution occurs in ILs. The present project was conducted to 1. REPORT...Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents Report Title ABSTRACT Over the

Ultraviolet light photobiology of the protozoan Tetrahymena pyriformis and chemical reactivation of DNA damage

International Nuclear Information System (INIS)

Wheeler, J.S.

1988-01-01

The tunable dye laser was developed in order to perform UV-B and UV-C (254-320 nm) action spectra studies on several different organisms. Using the laser, action spectra studies have been performed for Escherichia coli, Saccharomyces, Chlamydomonas, Caenorhabditis elegans, Paramecium, and Tetrahymena pyriformis. Studies generally indicate increasing LD 50 values with increasing wavelength. Two notable findings were made: (1) The action spectra does not follow the DNA absorption spectra at 280, 290 and 295 nm; (2) The repair competent/repair defective sensitization factor does not remain constant throughout the wavelength region. In addition it was found that the repair defective strain of E. coli, Bs-1, showed an increase in survival with increasing UV irradiation, at certain dose levels. Further experiments were designed to better characterize the reactivation. Tetrahymena were exposed to UV-C and reactivated with methyl methanesulfonate (MMS) and 4-nitro quinoline oxide (4-NQO). In both cases survival was seen to increase after chemical exposure. Likewise, UV-C was found to reactivate chemical damage (MMS)

The underlying toxicological mechanism of chemical mixtures: A case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum

International Nuclear Information System (INIS)

Tian, Dayong; Lin, Zhifen; Zhou, Xianghong; Yin, Daqiang

2013-01-01

Intracellular chemical reaction of chemical mixtures is one of the main reasons that cause synergistic or antagonistic effects. However, it still remains unclear what the influencing factors on the intracellular chemical reaction are, and how they influence on the toxicological mechanism of chemical mixtures. To reveal this underlying toxicological mechanism of chemical mixtures, a case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum was employed, and both their joint effects and mixture toxicity were observed. Then series of two-step linear regressions were performed to describe the relationships between joint effects, the expected additive toxicities and descriptors of individual chemicals (including concentrations, binding affinity to receptors, octanol/water partition coefficients). Based on the quantitative relationships, the underlying joint toxicological mechanisms were revealed. The result shows that, for mixtures with their joint effects resulting from intracellular chemical reaction, their underlying toxicological mechanism depends on not only their interaction with target proteins, but also their transmembrane actions and their concentrations. In addition, two generic points of toxicological mechanism were proposed including the influencing factors on intracellular chemical reaction and the difference of the toxicological mechanism between single reactive chemicals and their mixtures. This study provided an insight into the understanding of the underlying toxicological mechanism for chemical mixtures with intracellular chemical reaction. - Highlights: • Joint effects of nitriles and aldehydes at non-equitoxic ratios were determined. • A novel descriptor, ligand–receptor interaction energy (E binding ), was employed. • Quantitative relationships for mixtures were developed based on a novel descriptor. • The underlying toxic mechanism was revealed based on quantitative relationships. • Two generic

The underlying toxicological mechanism of chemical mixtures: A case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum

Energy Technology Data Exchange (ETDEWEB)

Tian, Dayong [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Department of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000 (China); Lin, Zhifen, E-mail: lzhifen@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Zhou, Xianghong [Department of Public Management, Tongji University, Shanghai 200092 (China); Yin, Daqiang [Key Laboratory of Yangtze River Water Environment, Ministry of Education, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)

2013-10-15

Intracellular chemical reaction of chemical mixtures is one of the main reasons that cause synergistic or antagonistic effects. However, it still remains unclear what the influencing factors on the intracellular chemical reaction are, and how they influence on the toxicological mechanism of chemical mixtures. To reveal this underlying toxicological mechanism of chemical mixtures, a case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum was employed, and both their joint effects and mixture toxicity were observed. Then series of two-step linear regressions were performed to describe the relationships between joint effects, the expected additive toxicities and descriptors of individual chemicals (including concentrations, binding affinity to receptors, octanol/water partition coefficients). Based on the quantitative relationships, the underlying joint toxicological mechanisms were revealed. The result shows that, for mixtures with their joint effects resulting from intracellular chemical reaction, their underlying toxicological mechanism depends on not only their interaction with target proteins, but also their transmembrane actions and their concentrations. In addition, two generic points of toxicological mechanism were proposed including the influencing factors on intracellular chemical reaction and the difference of the toxicological mechanism between single reactive chemicals and their mixtures. This study provided an insight into the understanding of the underlying toxicological mechanism for chemical mixtures with intracellular chemical reaction. - Highlights: • Joint effects of nitriles and aldehydes at non-equitoxic ratios were determined. • A novel descriptor, ligand–receptor interaction energy (E{sub binding}), was employed. • Quantitative relationships for mixtures were developed based on a novel descriptor. • The underlying toxic mechanism was revealed based on quantitative relationships. • Two

Modification of the finite element heat and mass transfer code (FEHM) to model multicomponent reactive transport

International Nuclear Information System (INIS)

Viswanathan, H.S.

1996-08-01

The finite element code FEHMN, developed by scientists at Los Alamos National Laboratory (LANL), is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developing hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent Kd model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The new chemical capabilities of FEHMN are illustrated by using Los Alamos National Laboratory's site scale model of Yucca Mountain to model two-dimensional, vadose zone 14 C transport. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect 14 C transport at Yucca Mountain. The simulations also prove that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies

Vortices generation in the reactive flow on the evaporative surface

Energy Technology Data Exchange (ETDEWEB)

Park, Cha Ryeom; Lee, Chang Jin [Konkuk University, Seoul (Korea, Republic of)

2015-02-15

Vortices generation and flow dynamics are investigated by a numerical calculation with LES methodology on the evaporative surface including chemical reactions. For simplicity, fuel is radially injected from the surface in order to decouple pyrolysis of solid fuel from the governing equation and consideration of heat transfer balance. Nevertheless its simple treatment of chemical reactions and fuel pyrolysis, numerical results captured very fundamental understandings in terms of averaged temperature, velocity profile, and mixture fraction distribution. Results showed that a well-defined turbulent velocity profile at the inlet becomes twisted and highly wrinkled in the downstream reaching the maximum velocity at far above the surface, where the flame is located. And the thickness of boundary layer increases in the downstream due to the enhanced interaction of axial flow and mass injection from the surface. Also, chemical reaction appears highly active and partially concentrated along the plane where flow condition is in stoichiometric. In particular, flame front locates at the surface where mixture fraction Z equals to 0.07. Flame front severely wrinkles in the downstream by the interaction with turbulences in the flow. Partial reactions on the flame front contribute to produce hot spots periodically in the downstream attaining the max temperature at the center of each spot. This may take the role of additional unsteady heat generations and pressure perturbations in the downstream. Future study will focus on the evolution of hot spots and pressure perturbations in the post chamber of lab scale hybrid rocket motors.

Flow-dependent directional growth of carbon nanotube forests by chemical vapor deposition

International Nuclear Information System (INIS)

Kim, Hyeongkeun; Park, Young Chul; Chun, Kyoung-Yong; Kim, Young-Jin; Choi, Jae-Boong; Kim, Keun Soo; Kang, Junmo; Hong, Byung Hee; Boo, Jin-Hyo

2011-01-01

We demonstrated that the structural formation of vertically aligned carbon nanotube (CNT) forests is primarily affected by the geometry-related gas flow, leading to the change of growth directions during the chemical vapor deposition (CVD) process. By varying the growing time, flow rate, and direction of the carrier gas, the structures and the formation mechanisms of the vertically aligned CNT forests were carefully investigated. The growth directions of CNTs are found to be highly dependent on the nonlinear local gas flows induced by microchannels. The angle of growth significantly changes with increasing gas flows perpendicular to the microchannel, while the parallel gas flow shows almost no effect. A computational fluid dynamics (CFD) model was employed to explain the flow-dependent growth of CNT forests, revealing that the variation of the local pressure induced by microchannels is an important parameter determining the directionality of the CNT growth. We expect that the present method and analyses would provide useful information to control the micro- and macrostructures of vertically aligned CNTs for various structural/electrical applications.

Flow-dependent directional growth of carbon nanotube forests by chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyeongkeun; Park, Young Chul; Chun, Kyoung-Yong; Kim, Young-Jin; Choi, Jae-Boong [School of Mechanical Engineering, Sungkyunkwan University, Suwon, 440-746 (Korea, Republic of); Kim, Keun Soo; Kang, Junmo; Hong, Byung Hee [SKKU Advanced Institute of Nanotechnology (SAINT) and Center for Human Interface Nano Technology (HINT), Sungkyunkwan University, Suwon, 440-746 (Korea, Republic of); Boo, Jin-Hyo, E-mail: byunghee@skku.edu, E-mail: boong33@skku.edu [Department of Chemistry, RIAN and Institute of Basic Science, Sungkyunkwan University, Suwon, 440-746 (Korea, Republic of)

2011-03-04

We demonstrated that the structural formation of vertically aligned carbon nanotube (CNT) forests is primarily affected by the geometry-related gas flow, leading to the change of growth directions during the chemical vapor deposition (CVD) process. By varying the growing time, flow rate, and direction of the carrier gas, the structures and the formation mechanisms of the vertically aligned CNT forests were carefully investigated. The growth directions of CNTs are found to be highly dependent on the nonlinear local gas flows induced by microchannels. The angle of growth significantly changes with increasing gas flows perpendicular to the microchannel, while the parallel gas flow shows almost no effect. A computational fluid dynamics (CFD) model was employed to explain the flow-dependent growth of CNT forests, revealing that the variation of the local pressure induced by microchannels is an important parameter determining the directionality of the CNT growth. We expect that the present method and analyses would provide useful information to control the micro- and macrostructures of vertically aligned CNTs for various structural/electrical applications.

A new particle-like method for high-speed flows with chemical non-equilibrium

Directory of Open Access Journals (Sweden)

Fábio Rodrigues Guzzo

2010-04-01

Full Text Available The present work is concerned with the numerical simulation of hypersonic blunt body flows with chemical non-equilibrium. New theoretical and numerical formulations for coupling the chemical reaction to the fluid dynamics are presented and validated. The fluid dynamics is defined for a stationary unstructured mesh and the chemical reaction process is defined for “finite quantities” moving through the stationary mesh. The fluid dynamics is modeled by the Euler equations and the chemical reaction rates by the Arrhenius law. Ideal gases are considered. The thermodynamical data are based on JANNAF tables and Burcat’s database. The algorithm proposed by Liou, known as AUSM+, is implemented in a cell-centered based finite volume method and in an unstructured mesh context. Multidimensional limited MUSCL interpolation method is used to perform property reconstructions and to achieve second-order accuracy in space. The minmod limiter is used. The second order accuracy, five stage, Runge-Kutta time-stepping scheme is employed to perform the time march for the fluid dynamics. The numerical code VODE, which is part of the CHEMKIN-II package, is adopted to perform the time integration for the chemical reaction equations. The freestream reacting fluid is composed of H2 and air at the stoichiometric ratio. The emphasis of the present paper is on the description of the new methodology for handling the coupling of chemical and fluid mechanic processes, and its validation by comparison with the standard time-splitting procedure. The configurations considered are the hypersonic flow over a wedge, in which the oblique detonation wave is induced by an oblique shock wave, and the hypersonic flow over a blunt body. Differences between the solutions obtained with each formulation are presented and discussed, including the effects of grid refinement in each case. The primary objective of such comparisons is the validation of the proposed methodology. Moreover, for

Online quench-flow electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for elucidating kinetic and chemical enzymatic reaction mechanisms.

Science.gov (United States)

Clarke, David J; Stokes, Adam A; Langridge-Smith, Pat; Mackay, C Logan

2010-03-01

We have developed an automated quench-flow microreactor which interfaces directly to an electrospray ionization (ESI) mass spectrometer. We have used this device in conjunction with ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to demonstrate the potential of this approach for studying the mechanistic details of enzyme reactions. For the model system chosen to test this device, namely, the pre-steady-state hydrolysis of p-nitrophenyl acetate by the enzyme chymotrypsin, the kinetic parameters obtained are in good agreement with those in the literature. To our knowledge, this is the first reported use of online quench-flow coupled with FTICR MS. Furthermore, we have exploited the power of FTICR MS to interrogate the quenched covalently bound enzyme intermediate using top-down fragmentation. The accurate mass capabilities of FTICR MS permitted the nature of the intermediate to be assigned with high confidence. Electron capture dissociation (ECD) fragmentation allowed us to locate the intermediate to a five amino acid section of the protein--which includes the known catalytic residue, Ser(195). This experimental approach, which uniquely can provide both kinetic and chemical details of enzyme mechanisms, is a potentially powerful tool for studies of enzyme catalysis.

Chemical reactivation of resin-embedded pHuji adds red for simultaneous two-color imaging with EGFP

Science.gov (United States)

Guo, Wenyan; Liu, Xiuli; Liu, Yurong; Gang, Yadong; He, Xiaobin; Jia, Yao; Yin, Fangfang; Li, Pei; Huang, Fei; Zhou, Hongfu; Wang, Xiaojun; Gong, Hui; Luo, Qingming; Xu, Fuqiang; Zeng, Shaoqun

2017-01-01

The pH-sensitive fluorescent proteins enabling chemical reactivation in resin are useful tools for fluorescence microimaging. EGFP or EYFP is good for such applications. For simultaneous two-color imaging, a suitable red fluorescent protein is an urgent need. Here a pH-sensitive red fluorescent protein, pHuji, is selected and verified to remain pH-sensitive in HM20 resin. We observe 183% fluorescence intensity of pHuji in resin-embeded mouse brain and 29.08-fold fluorescence intensity of reactivated pHuji compared to the quenched state. pHuji and EGFP can be quenched and chemically reactivated simultaneously in resin, thus enabling simultaneous two-color micro-optical sectioning tomography of resin-embedded mouse brain. This method may greatly facilitate the visualization of neuronal morphology and neural circuits to promote understanding of the structure and function of the brain. PMID:28717566

Mechanisms of Kaposi's Sarcoma-Associated Herpesvirus Latency and Reactivation

Directory of Open Access Journals (Sweden)

Fengchun Ye

2011-01-01

Full Text Available The life cycle of Kaposi's sarcoma-associated herpesvirus (KSHV consists of latent and lytic replication phases. During latent infection, only a limited number of KSHV genes are expressed. However, this phase of replication is essential for persistent infection, evasion of host immune response, and induction of KSHV-related malignancies. KSHV reactivation from latency produces a wide range of viral products and infectious virions. The resulting de novo infection and viral lytic products modulate diverse cellular pathways and stromal microenvironment, which promote the development of Kaposi's sarcoma (KS. The mechanisms controlling KSHV latency and reactivation are complex, involving both viral and host factors, and are modulated by diverse environmental factors. Here, we review the cellular and molecular basis of KSHV latency and reactivation with a focus on the most recent advancements in the field.

CISM course on stochastic methods in fluid mechanics

CERN Document Server

Chibbaro, Sergio

2013-01-01

Since their first introduction in natural sciences through the work of Einstein on Brownian motion in 1905 and further works, in particular by Langevin, Smoluchowski and others, stochastic processes have been used in several areas of science and technology. For example, they have been applied in chemical studies, or in fluid turbulence and for combustion and reactive flows. The articles in this book provide a general and unified framework in which stochastic processes are presented as modeling tools for various issues in engineering, physics and chemistry, with particular focus on fluid mechan

Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

Energy Technology Data Exchange (ETDEWEB)

Bergren, Adam Johan [Iowa State Univ., Ames, IA (United States)

2006-01-01

Electroanalytical chemistry is often utilized in chemical analysis and Fundamental studies. Important advances have been made in these areas since the advent of chemically modified electrodes: the coating of an electrode with a chemical film in order to impart desirable, and ideally, predictable properties. These procedures enable the exploitation of unique reactivity patterns. This dissertation presents studies that investigate novel reaction mechanisms at self-assembled monolayers on gold. In particular, a unique electrochemical current amplification scheme is detailed that relies on a selective electrode to enable a reactivity pattern that results in regeneration of the analyte (redox recycling). This regenerating reaction can occur up to 250 times for each analyte molecule, leading to a notable enhancement in the observed current. The requirements of electrode selectivity and the resulting amplification and detection limit improvements are described with respect to the heterogeneous and homogeneous electron transfer rates that characterize the system. These studies revealed that the heterogeneous electrolysis of the analyte should ideally be electrochemically reversible, while that for the regenerating agent should be held to a low level. Moreover, the homogeneous reaction that recycles the analyte should occur at a rapid rate. The physical selectivity mechanism is also detailed with respect to the properties of the electrode and redox probes utilized. It is shown that partitioning of the analyte into/onto the adlayer leads to the extraordinary selectivity of the alkanethiolate monolayer modified electrode. Collectively, these studies enable a thorough understanding of the complex electrode mechanism required for successful redox recycling amplification systems, Finally, in a separate (but related) study, the effect of the akyl chain length on the heterogeneous electron transfer behavior of solution-based redox probes is reported, where an odd-even oscillation

Mechanism governing nanoparticle flow behaviour in porous media: insight for enhanced oil recovery applications

Science.gov (United States)

Agi, Augustine; Junin, Radzuan; Gbadamosi, Afeez

2018-06-01

Nanotechnology has found its way to petroleum engineering, it is well-accepted path in the oil and gas industry to recover more oil trapped in the reservoir. But the addition of nanoparticles to a liquid can result in the simplest flow becoming complex. To understand the working mechanism, there is a need to study the flow behaviour of these particles. This review highlights the mechanism affecting the flow of nanoparticles in porous media as it relates to enhanced oil recovery. The discussion focuses on chemical-enhanced oil recovery, a review on laboratory experiment on wettability alteration, effect of interfacial tension and the stability of emulsion and foam is discussed. The flow behaviour of nanoparticles in porous media was discussed laying emphasis on the physical aspect of the flow, the microscopic rheological behaviour and the adsorption of the nanoparticles. It was observed that nanofluids exhibit Newtonian behaviour at low shear rate and non-Newtonian behaviour at high shear rate. Gravitational and capillary forces are responsible for the shift in wettability from oil-wet to water-wet. The dominant mechanisms of foam flow process were lamellae division and bubble to multiple bubble lamellae division. In a water-wet system, the dominant mechanism of flow process and residual oil mobilization are lamellae division and emulsification, respectively. Whereas in an oil-wet system, the generation of pre-spinning continuous gas foam was the dominant mechanism. The literature review on oil displacement test and field trials indicates that nanoparticles can recover additional oil. The challenges encountered have opened new frontier for research and are highlighted herein.

Dissociative recombination in reactive flows related to planetary atmospheric entries

Directory of Open Access Journals (Sweden)

Bultel Arnaud

2015-01-01

Full Text Available The Dissociative Recombination (DR processes play a significant role in plasma chemistry. This article illustrates this role from the modeling point of view in the case of reactive flows related to atmospheric entry plasmas. Two situations are investigated, for which the studied plasma is nitrogen. The first configuration corresponds to the relaxation process behind a strong shock wave moving at high Mach number in a shock tube, the second one to the recombination taking place in an expanding plasma flowing in a diverging nozzle. In both cases, the collisional-radiative model CoRaM-N2, involving N2, N, N2+, N+ and electrons, is implemented in an Eulerian 1D code able to compute the aerodynamic fields; calculations are performed in standard conditions. We show that, according to the rate coefficients used for the DR processes, the population density of the charged species especially N2+ is strongly modified only for the post-shock flow.

Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

International Nuclear Information System (INIS)

Roh, Heui-Seol

2015-01-01

Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

Directory of Open Access Journals (Sweden)

Zhengde Tan

2013-01-01

Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

Oscillatory flow chemical reactors

Directory of Open Access Journals (Sweden)

Slavnić Danijela S.

2014-01-01

Full Text Available Global market competition, increase in energy and other production costs, demands for high quality products and reduction of waste are forcing pharmaceutical, fine chemicals and biochemical industries, to search for radical solutions. One of the most effective ways to improve the overall production (cost reduction and better control of reactions is a transition from batch to continuous processes. However, the reactions of interests for the mentioned industry sectors are often slow, thus continuous tubular reactors would be impractically long for flow regimes which provide sufficient heat and mass transfer and narrow residence time distribution. The oscillatory flow reactors (OFR are newer type of tube reactors which can offer solution by providing continuous operation with approximately plug flow pattern, low shear stress rates and enhanced mass and heat transfer. These benefits are the result of very good mixing in OFR achieved by vortex generation. OFR consists of cylindrical tube containing equally spaced orifice baffles. Fluid oscillations are superimposed on a net (laminar flow. Eddies are generated when oscillating fluid collides with baffles and passes through orifices. Generation and propagation of vortices create uniform mixing in each reactor cavity (between baffles, providing an overall flow pattern which is close to plug flow. Oscillations can be created by direct action of a piston or a diaphragm on fluid (or alternatively on baffles. This article provides an overview of oscillatory flow reactor technology, its operating principles and basic design and scale - up characteristics. Further, the article reviews the key research findings in heat and mass transfer, shear stress, residence time distribution in OFR, presenting their advantages over the conventional reactors. Finally, relevant process intensification examples from pharmaceutical, polymer and biofuels industries are presented.

Systematic reduction of complex tropospheric chemical mechanisms, Part II: Lumping using a time-scale based approach

Directory of Open Access Journals (Sweden)

L. E. Whitehouse

2004-01-01

Full Text Available This paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0 has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA, a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations.

Mineralogy controls on reactive transport of Marcellus Shale waters.

Science.gov (United States)

Cai, Zhang; Wen, Hang; Komarneni, Sridhar; Li, Li

2018-07-15

Produced or flowback waters from Marcellus Shale gas extraction (MSWs) typically are highly saline and contain chemicals including trace metals, which pose significant concerns on water quality. The natural attenuation of MSW chemicals in groundwater is poorly understood due to the complex interactions between aquifer minerals and MSWs, limiting our capabilities to monitor and predict. Here we combine flow-through experiments and process-based reactive transport modeling to understand mechanisms and quantify the retention of MSW chemicals in a quartz (Qtz) column, a calcite-rich (Cal) column, and a clay-rich (Vrm, vermiculite) column. These columns were used to represent sand, carbonate, and clay-rich aquifers. Results show that the types and extent of water-rock interactions differ significantly across columns. Although it is generally known that clay-rich media retard chemicals and that quartz media minimize water-rock interactions, results here have revealed insights that differ from previous thoughts. We found that the reaction mechanisms are much more complex than merely sorption and mineral precipitation. In clay rich media, trace metals participate in both ion exchange and mineral precipitation. In fact, the majority of metals (~50-90%) is retained in the solid via mineral precipitation, which is surprising because we typically expect the dominance of sorption in clay-rich aquifers. In the Cal column, trace metals are retained not only through precipitation but also solid solution partitioning, leading to a total of 75-99% retention. Even in the Qtz column, trace metals are retained at unexpectedly high percentages (~20-70%) due to precipitation. The reactive transport model developed here quantitatively differentiates the relative importance of individual processes, and bridges a limited number of experiments to a wide range of natural conditions. This is particularly useful where relatively limited knowledge and data prevent the prediction of complex rock

Integrated Microfluidic Membrane Transistor Utilizing Chemical Information for On-Chip Flow Control

Science.gov (United States)

Frank, Philipp; Schreiter, Joerg; Haefner, Sebastian; Paschew, Georgi; Voigt, Andreas; Richter, Andreas

2016-01-01

Microfluidics is a great enabling technology for biology, biotechnology, chemistry and general life sciences. Despite many promising predictions of its progress, microfluidics has not reached its full potential yet. To unleash this potential, we propose the use of intrinsically active hydrogels, which work as sensors and actuators at the same time, in microfluidic channel networks. These materials transfer a chemical input signal such as a substance concentration into a mechanical output. This way chemical information is processed and analyzed on the spot without the need for an external control unit. Inspired by the development electronics, our approach focuses on the development of single transistor-like components, which have the potential to be used in an integrated circuit technology. Here, we present membrane isolated chemical volume phase transition transistor (MIS-CVPT). The device is characterized in terms of the flow rate from source to drain, depending on the chemical concentration in the control channel, the source-drain pressure drop and the operating temperature. PMID:27571209

Integrated Microfluidic Membrane Transistor Utilizing Chemical Information for On-Chip Flow Control.

Science.gov (United States)

Frank, Philipp; Schreiter, Joerg; Haefner, Sebastian; Paschew, Georgi; Voigt, Andreas; Richter, Andreas

2016-01-01

Microfluidics is a great enabling technology for biology, biotechnology, chemistry and general life sciences. Despite many promising predictions of its progress, microfluidics has not reached its full potential yet. To unleash this potential, we propose the use of intrinsically active hydrogels, which work as sensors and actuators at the same time, in microfluidic channel networks. These materials transfer a chemical input signal such as a substance concentration into a mechanical output. This way chemical information is processed and analyzed on the spot without the need for an external control unit. Inspired by the development electronics, our approach focuses on the development of single transistor-like components, which have the potential to be used in an integrated circuit technology. Here, we present membrane isolated chemical volume phase transition transistor (MIS-CVPT). The device is characterized in terms of the flow rate from source to drain, depending on the chemical concentration in the control channel, the source-drain pressure drop and the operating temperature.

Reactivity feedback evaluation of material relocations in the CABRI-1 experiments with fuel worth distributions from SNR-300

International Nuclear Information System (INIS)

Royl, P.; Pfrang, W.; Struwe, D.

1991-01-01

The fuel relocations from the CABRI-1 experiments with irradiated fuel that had been evaluated from the hodoscope measurements were used together with fuel reactivity worth distributions from the SNR-300 to estimate the reactivity effect which these motions would have if they occurred in SNR-300 at the same relative distance to the peak power as in CABRI. The procedure for the reactivity evaluation is outlined including the assumptions made for fuel mass conservation. The results show that the initial fuel motion yields always negative reactivities. They also document the mechanism for a temporary reactivity increase by in-pin fuel flow in some transient overpower tests. This mechanism, however, never dominates, because material accumulates always sufficiently above the peak power point. Thus, the late autocatalytic amplifications of voiding induced power excursions by compactive in-pin fuel flow, that had been simulated in bounding loss of flow analyses for SNR-300, have no basis at all when considering the results from the CABRI-1 experiments

Chemical reactivity of potential ferrocyanide precipitates in Hanford tanks with nitrates and nitrites

International Nuclear Information System (INIS)

Scheele, R.D.; Burger, L.L.; Tingey, J.M.; Hallen, R.T.; Lilga, M.A.

1992-01-01

Ferrocyanide-bearing wastes were produced at the Hanford Site during the 1950s. Safe storage of these wastes has recently drawn increased attention. As a result of these concerns, the Pacific Northwest Laboratory was chartered to investigate the chemical reactivity and explosivity of the ferrocyanide-bearing wastes. We have investigated the thermal sensitivity of synthetic wastes and ferrocyanides and observed oxidation at 130 deg. C and explosions down to 295 deg. C. Coupled with thermodynamic calculations, these thermal studies have also shown a dependence of the reactivity on the synthetic waste composition, which is dependent on the solids settling behavior. (author)

How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

Science.gov (United States)

Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

2018-05-01

We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25-30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this work, we suggest that water vapor

Breakage mechanics for granular materials in surface-reactive environments

Science.gov (United States)

Zhang, Yida; Buscarnera, Giuseppe

2018-03-01

It is known that the crushing behaviour of granular materials is sensitive to the state of the fluids occupying the pore space. Here, a thermomechanical theory is developed to link such macroscopic observations with the physico-chemical processes operating at the microcracks of individual grains. The theory relies on the hypothesis that subcritical fracture propagation at intra-particle scale is the controlling mechanism for the rate-dependent, water-sensitive compression of granular specimens. First, the fracture of uniaxially compressed particles in surface-reactive environments is studied in light of irreversible thermodynamics. Such analysis recovers the Gibbs adsorption isotherm as a central component linking the reduction of the fracture toughness of a solid to the increase of vapour concentration. The same methodology is then extended to assemblies immersed in wet air, for which solid-fluid interfaces have been treated as a separate phase. It is shown that this choice brings the solid surface energy into the dissipation equations of the granular matrix, thus providing a pathway to (i) integrate the Gibbs isotherm with the continuum description of particle assemblies and (ii) reproduce the reduction of their yield strength in presence of high relative humidity. The rate-effects involved in the propagation of cracks and the evolution of breakage have been recovered by considering non-homogenous dissipation potentials associated with the creation of surface area at both scales. It is shown that the proposed model captures satisfactorily the compression response of different types of granular materials subjected to varying relative humidity. This result was achieved simply by using parameters based on the actual adsorption characteristics of the constituting minerals. The theory therefore provides a physically sound and thermodynamically consistent framework to study the behaviour of granular solids in surface-reactive environments.

Arteriolar oxygen reactivity: where is the sensor and what is the mechanism of action?

Science.gov (United States)

2016-01-01

Abstract Arterioles in the peripheral microcirculation are exquisitely sensitive to changes in PO2 in their environment: increases in PO2 cause vasoconstriction while decreases in PO2 result in vasodilatation. However, the cell type that senses O2 (the O2 sensor) and the signalling pathway that couples changes in PO2 to changes in arteriolar tone (the mechanism of action) remain unclear. Many (but not all) ex vivo studies of isolated cannulated resistance arteries and large, first‐order arterioles support the hypothesis that these vessels are intrinsically sensitive to PO2 with the smooth muscle, endothelial cells, or red blood cells serving as the O2 sensor. However, in situ studies testing these hypotheses in downstream arterioles have failed to find evidence of intrinsic O2 sensitivity, and instead have supported the idea that extravascular cells sense O2. Similarly, ex vivo studies of isolated, cannulated resistance arteries and large first‐order arterioles support the hypotheses that O2‐dependent inhibition of production of vasodilator cyclooxygenase products or O2‐dependent destruction of nitric oxide mediates O2 reactivity of these upstream vessels. In contrast, most in vivo studies of downstream arterioles have disproved these hypotheses and instead have provided evidence supporting the idea that O2‐dependent production of vasoconstrictors mediates arteriolar O2 reactivity, with significant regional heterogeneity in the specific vasoconstrictor involved. Oxygen‐induced vasoconstriction may serve as a protective mechanism to reduce the oxidative burden to which a tissue is exposed, a process that is superimposed on top of the local mechanisms which regulate tissue blood flow to meet a tissue's metabolic demand. PMID:27324312

Chemical and mechanical efficiencies of molecular motors and implications for motor mechanisms

International Nuclear Information System (INIS)

Wang Hongyun

2005-01-01

Molecular motors operate in an environment dominated by viscous friction and thermal fluctuations. The chemical reaction in a motor may produce an active force at the reaction site to directly move the motor forward. Alternatively a molecular motor may generate a unidirectional motion by rectifying thermal fluctuations using free energy barriers established in the chemical reaction. The reaction cycle has many occupancy states, each having a different effect on the motor motion. The average effect of the chemical reaction on the motor motion can be characterized by the motor potential profile. The biggest advantage of studying the motor potential profile is that it can be reconstructed from the time series of motor positions measured in single-molecule experiments. In this paper, we use the motor potential profile to express the Stokes efficiency as the product of the chemical efficiency and the mechanical efficiency. We show that both the chemical and mechanical efficiencies are bounded by 100% and, thus, are properly defined efficiencies. We discuss implications of high efficiencies for motor mechanisms: a mechanical efficiency close to 100% implies that the motor potential profile is close to a constant slope; a chemical efficiency close to 100% implies that (i) the chemical transitions are not slower than the mechanical motion and (ii) the equilibrium constant of each chemical transition is close to one

Chemical-potential flow equations for graphene with Coulomb interactions

Science.gov (United States)

Fräßdorf, Christian; Mosig, Johannes E. M.

2018-06-01

We calculate the chemical potential dependence of the renormalized Fermi velocity and static dielectric function for Dirac quasiparticles in graphene nonperturbatively at finite temperature. By reinterpreting the chemical potential as a flow parameter in the spirit of the functional renormalization group (fRG) we obtain a set of flow equations, which describe the change of these functions upon varying the chemical potential. In contrast to the fRG the initial condition of the flow is nontrivial and has to be calculated separately. Our results are consistent with a charge carrier-independent Fermi velocity v (k ) for small densities n ≲k2/π , supporting the comparison of the zero-density fRG calculation of Bauer et al. [Phys. Rev. B 92, 121409 (2015), 10.1103/PhysRevB.92.121409], with the experiment of Elias et al. [Nat. Phys. 7, 701 (2011), 10.1038/nphys2049].

Chemical kinetics and reaction mechanism

International Nuclear Information System (INIS)

Jung, Ou Sik; Park, Youn Yeol

1996-12-01

This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

Science.gov (United States)

Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

2015-01-01

Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

Mechanisms of large strain, high strain rate plastic flow in the explosively driven collapse of Ni-Al laminate cylinders

International Nuclear Information System (INIS)

Olney, K L; Chiu, P H; Nesterenko, V F; Higgins, A; Serge, M; Weihs, T P; Fritz, G; Stover, A; Benson, D J

2014-01-01

Ni-Al laminates have shown promise as reactive materials due to their high energy release through intermetallic reaction. In addition to the traditional ignition methods, the reaction may be initiated in hot spots that can be created during mechanical loading. The explosively driven thick walled cylinder (TWC) technique was performed on two Ni-Al laminates composed of thin foil layers with different mesostructues: concentric and corrugated. These experiments were conducted to examine how these materials accommodate large plastic strain under high strain rates. Finite element simulations of these specimens with mesostuctures digitized from the experimental samples were conducted to provide insight into the mesoscale mechanisms of plastic flow. The dependence of dynamic behaviour on mesostructure may be used to tailor the hot spot formation and therefore the reactivity of the material system.

Inactivation of Escherichia coli on blueberries using cold plasma with chemical augmentation inside a partial vacuum

Science.gov (United States)

Justification: The mechanism by which cold plasma inactivates pathogens is through the production of free reactive chemical species. Unfortunately, the most reactive chemical species have the shortest half-life. In a vacuum their half-life is believed to be prolonged. Additionally, these reactive sp...

Reactive Spark Plasma Sintering and Mechanical Properties of Zirconium Diboride–Titanium Diboride Ultrahigh Temperature Ceramic Solid Solutions

Directory of Open Access Journals (Sweden)

Karthiselva N. S.

2016-09-01

Full Text Available Ultrahigh temperature ceramics (UHTCs such as diborides of zirconium, hafnium tantalum and their composites are considered to be the candidate materials for thermal protection systems of hypersonic vehicles due to their exceptional combination of physical, chemical and mechanical properties. A composite of ZrB2-TiB2 is expected to have better properties. In this study, an attempt has been made to fabricate ZrB2-TiB2 ceramics using mechanically activated elemental powders followed by reactive spark plasma sintering (RSPS at 1400 °C. Microstructure and phase analysis was carried out using X-ray diffractometer (XRD and electron microscopy to understand microstructure evolution. Fracture toughness and hardness were evaluated using indentation methods. Nanoindentation was used to measure elastic modulus. Compressive strength of the composites has been reported.

Flow Type Bio-Chemical Calorimeter with Micro Differential Thermopile Sensor.

Science.gov (United States)

Saito, Masataka; Nakabeppu, Osamu

2015-04-01

Bio-chemical calorimeters with a MEMS (Micro-Electro-Mechanical Systems) thermopile sensor have been studied for monitoring detailed processes of the biochemical reactions of a minute sample with a high temporal resolution. The bio-calorimeters are generally divided into a batch-type and a flow-type. We developed a highly sensitive batch-type calorimeter which can detect a 100 nW level thermal reaction. However it shows a long settling time of 2 hours because of the heat capacity of a whole calorimeter. Thus, the flow-type calorimeters in passive and active mode have been studied for measuring the thermal reactions in an early stage after starting an analysis. The flow-type calorimeter consists of the MEMS differential thermopile sensor, a pair of micro channel reactor in a PDMS (polydimethylsiloxane) sheet in a three-fold thermostat chamber. The calorimeter in the passive mode was tested with dilution reactions of ethanol to water and NaCl aqueous solution to water. It was shown that the calorimeter detects exo- and endothermic reaction over 250 nW at solution flow rate of 0.05 ~ 1 µl/min with a settling time of about 4 minutes. In the active mode, a response test was conducted by using heat removal by water flow from the reactor channel. The active calorimetry enhances the response time about three to four times faster.

Pay-as-bid based reactive power market

International Nuclear Information System (INIS)

Amjady, N.; Rabiee, A.; Shayanfar, H.A.

2010-01-01

In energy market clearing, the offers are stacked in increasing order and the offer that intersects demand curve, determines the market clearing price (MCP). In reactive power market, the location of reactive power compensator is so important. A low cost reactive producer may not essentially be favorable if it is far from the consumer. Likewise, a high cost local reactive compensator at a heavily loaded demand center of network could be inevitably an alternative required to produce reactive power to maintain the integrity of power system. Given the background, this paper presents a day-ahead reactive power market based on pay-as-bid (PAB) mechanism. Generators expected payment function (EPF) is used to construct a bidding framework. Then, total payment function (TPF) of generators is used as the objective function of optimal power flow (OPF) problem to clear the PAB based market. The CIGRE-32 bus test system is used to examine the effectiveness of the proposed reactive power market.

Pay-as-bid based reactive power market

Energy Technology Data Exchange (ETDEWEB)

Amjady, N. [Department of Electrical Engineering, Semnan University, Semnan (Iran, Islamic Republic of); Rabiee, A., E-mail: Rabiee@iust.ac.i [Center of Excellence for Power System Automation and Operation, Department of Electrical Engineering, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Shayanfar, H.A. [Center of Excellence for Power System Automation and Operation, Department of Electrical Engineering, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)

2010-02-15

In energy market clearing, the offers are stacked in increasing order and the offer that intersects demand curve, determines the market clearing price (MCP). In reactive power market, the location of reactive power compensator is so important. A low cost reactive producer may not essentially be favorable if it is far from the consumer. Likewise, a high cost local reactive compensator at a heavily loaded demand center of network could be inevitably an alternative required to produce reactive power to maintain the integrity of power system. Given the background, this paper presents a day-ahead reactive power market based on pay-as-bid (PAB) mechanism. Generators expected payment function (EPF) is used to construct a bidding framework. Then, total payment function (TPF) of generators is used as the objective function of optimal power flow (OPF) problem to clear the PAB based market. The CIGRE-32 bus test system is used to examine the effectiveness of the proposed reactive power market.

Cardiovascular reactivity as a mechanism linking child trauma to adolescent psychopathology

Science.gov (United States)

Heleniak, Charlotte; McLaughlin, Katie A.; Ormel, Johan; Riese, Harriette

2016-01-01

Alterations in physiological reactivity to stress are argued to be central mechanisms linking adverse childhood environmental experiences to internalizing and externalizing psychopathology. Childhood trauma exposure may influence physiological reactivity to stress in distinct ways from other forms of childhood adversity. This study applied a novel theoretical model to investigate the impact of childhood trauma on cardiovascular stress reactivity – the biopsychosocial model of challenge and threat. This model suggests that inefficient cardiovascular responses to stress – a threat as opposed to challenge profile – are characterized by blunted cardiac output (CO) reactivity and increased vascular resistance. We examined whether childhood trauma exposure predicted an indicator of the threat profile of cardiovascular reactivity and whether such a pattern was associated with adolescent psychopathology in a population-representative sample of 488 adolescents (M = 16.17 years old, 49.2% boys) in the TRacking Adolescents’ Individual Lives Survey (TRAILS). Exposure to trauma was associated with both internalizing and externalizing symptoms and a pattern of cardiovascular reactivity consistent with the threat profile, including blunted CO reactivity during a social stress task. Blunted CO reactivity, in turn, was positively associated with externalizing, but not internalizing symptoms and mediated the link between trauma and externalizing psychopathology. None of these associations varied by gender. The biopsychosocial model of challenge and threat provides a novel theoretical framework for understanding disruptions in physiological reactivity to stress following childhood trauma exposure, revealing a potential pathway linking such exposure with externalizing problems in adolescents. PMID:27568327

Effects of chemical contamination on HDPE - thermo-mechanical and characterisation properties

International Nuclear Information System (INIS)

Ashraf, G.

2002-01-01

Studying the effects of chemical contamination on HDPE is an important precursor in recycling of plastic packaging and polymer reprocessing. This research involves and discusses the results of an in-depth investigation into the effects of chemically contaminating, using various acids, commercial grade high density polyethylene (HDPE) used commonly in packaging applications. An extensive formulation study was conducted and it became obvious that in some cases degradation had occurred to HDPE when chemically contaminated with particular functional group types. The functional groups in contaminated HDPE were successfully identified. A variety of analytical techniques such as Fourier transform Infra-red spectroscopy, X-ray Florescence, x-ray photo electron spectroscopy could identify compounds such as HCl acid, HNO/sub 3/ acid and other related contaminants. Some chemical additives had effects on the mechanical and thermal properties when added in the most appropriate concentration. The results have shown lower tensile modulus and strength tensile elongation, lower modular weight, melt flow index and crystallinity. The amount of contaminant concentration, the type of chemical functional groups used and the type of test selected to affect degradation are important factors in proving the effects of chemical contamination on HDPE in the melt state. (author)

Topological fluid mechanics of Axisymmetric Flow

DEFF Research Database (Denmark)

Brøns, Morten

1998-01-01

Topological fluid mechanics in the sense of the present paper is the study and classification of flow patterns close to a critical point. Here we discuss the topology of steady viscous incompressible axisymmetric flows in the vicinity of the axis. Following previous studies the velocity field v...... to the authors knowledge has not been used systematically to high orders in topological fluid mechanics. We compare the general results with experimental and computational results on the Vogel-Ronneberg flow. We show that the topology changes observed when recirculating bubbles on the vortex axis are created...

Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry.

Science.gov (United States)

Domingo, Luis R

2016-09-30

A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

Fluid flow for chemical and process engineers

CERN Document Server

Holland, F

1995-01-01

This major new edition of a popular undergraduate text covers topics of interest to chemical engineers taking courses on fluid flow. These topics include non-Newtonian flow, gas-liquid two-phase flow, pumping and mixing. It expands on the explanations of principles given in the first edition and is more self-contained. Two strong features of the first edition were the extensive derivation of equations and worked examples to illustrate calculation procedures. These have been retained. A new extended introductory chapter has been provided to give the student a thorough basis to understand the methods covered in subsequent chapters.

Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

International Nuclear Information System (INIS)

Schatz, G.C.; Kuppermann, A.

1980-01-01

We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v-1 processes dominating

Quantum chemical approaches: semiempirical molecular orbital and hybrid quantum mechanical/molecular mechanical techniques.

Science.gov (United States)

Bryce, Richard A; Hillier, Ian H

2014-01-01

The use of computational quantum chemical methods to aid drug discovery is surveyed. An overview of the various computational models spanning ab initio, density function theory, semiempirical molecular orbital (MO), and hybrid quantum mechanical (QM)/molecular mechanical (MM) methods is given and their strengths and weaknesses are highlighted, focussing on the challenge of obtaining the accuracy essential for them to make a meaningful contribution to drug discovery. Particular attention is given to hybrid QM/MM and semiempirical MO methods which have the potential to yield the necessary accurate predictions of macromolecular structure and reactivity. These methods are shown to have advanced the study of many aspects of substrate-ligand interactions relevant to drug discovery. Thus, the successful parametrization of semiempirical MO methods and QM/MM methods can be used to model noncovalent substrate-protein interactions, and to lead to improved scoring functions. QM/MM methods can be used in crystal structure refinement and are particularly valuable for modelling covalent protein-ligand interactions and can thus aid the design of transition state analogues. An extensive collection of examples from the areas of metalloenzyme structure, enzyme inhibition, and ligand binding affinities and scoring functions are used to illustrate the power of these techniques.

Linking new information to a reactivated memory requires consolidation and not reconsolidation mechanisms.

Directory of Open Access Journals (Sweden)

2005-09-01

Full Text Available A new memory is initially labile and becomes stabilized through a process of consolidation, which depends on gene expression. Stable memories, however, can again become labile if reactivated by recall and require another phase of protein synthesis in order to be maintained. This process is known as reconsolidation. The functional significance of the labile phase of reconsolidation is unknown; one hypothesis proposes that it is required to link new information with reactivated memories. Reconsolidation is distinct from the initial consolidation, and one distinction is that the requirement for specific proteins or general protein synthesis during the two processes occurs in different brain areas. Here, we identified an anatomically distinctive molecular requirement that doubly dissociates consolidation from reconsolidation of an inhibitory avoidance memory. We then used this requirement to investigate whether reconsolidation and consolidation are involved in linking new information with reactivated memories. In contrast to what the hypothesis predicted, we found that reconsolidation does not contribute to the formation of an association between new and reactivated information. Instead, it recruits mechanisms similar to those underlying consolidation of a new memory. Thus, linking new information to a reactivated memory is mediated by consolidation and not reconsolidation mechanisms.

Quantum dots assisted photocatalysis for the chemiluminometric determination of chemical oxygen demand using a single interface flow system

Energy Technology Data Exchange (ETDEWEB)

Silvestre, Cristina I.C.; Frigerio, Christian [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal); Santos, Joao L.M., E-mail: joaolms@ff.up.pt [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal); Lima, Jose L.F.C. [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal)

2011-08-12

Highlights: {yields} A novel flow method for the determination of chemical oxygen demand is proposed. {yields} CdTe nanocrystals are irradiated with UV light to generate strong oxidizing species. {yields} Reactive species promote a fast catalytic degradation of organic matter. {yields} Luminol is used as a chemiluminescence probe for indirect COD assessment. {yields} A single interface flow system was implemented to automate the assays. - Abstract: A novel flow method for the determination of chemical oxygen demand (COD) is proposed in this work. It relies on the combination of a fully automated single interface flow system, an on-line UV photocatalytic unit and quantum dot (QD) nanotechnology. The developed approach takes advantage of CdTe nanocrystals capacity to generate strong oxidizing species upon irradiation with UV light, which fostered a fast catalytic degradation of the organic compounds. Luminol was used as a chemiluminescence (CL) probe for indirect COD assessment, since it is easily oxidized by the QD generated species yielding a strong CL emission that is quenched in the presence of the organic matter. The proposed methodology allowed the determination of COD concentrations between 1 and 35 mg L{sup -1}, with good precision (R.S.D. < 1.1%, n = 3) and a sampling frequency of about 33 h{sup -1}. The procedure was applied to the determination of COD in wastewater certified reference materials and the obtained results showed an excellent agreement with the certified values.

Mechanical properties of chemically modified portuguese pinewood

OpenAIRE

Lopes, Duarte B; Mai, Carsten; Militz, Holger

2014-01-01

To turn wood into a construction material with enhanced properties, many methods of chemical modification have been developed in the last few decades. In this work, mechanical properties of pine wood were chemically modified, compared and evaluated. Maritime pine wood (Pinus pinaster) was modified with four chemical processes: 1,3-dimethylol-4,5- dihydroxyethyleneurea, N-methylol melamine formaldehyde, tetra-alkoxysilane and wax. The following mechanical properties were assessed experiment...

Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

Directory of Open Access Journals (Sweden)

C. W. Spicer

1994-08-01

Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

Observation by flow 1H NMR and dimerization kinetics and products of reactive ortho-quinodimethanes and benzocyclobutadiene

International Nuclear Information System (INIS)

Fischer, D.

1990-01-01

The reactive o-quinodimethanes, 1,2-dimethylene-1,2-dihydronaphthalene (9) and o-xylylene (1) were observed by flow 1 H NMR spectroscopy at room temperature. The 1 H NMR spectrum of 9 was obtained in the absence of precursor and dimers. However, the 1 H NMR spectrum of the more reactive 1, generated in a similar manner from [o-((trimethylsilyl)methyl)benzyl]trimethylammonium iodide (5.) could be obtained only in the presence of its stable [4 + 2] and [4 + 4] dimers. The dimerization kinetics of 3-methyl- (5'), 3,6-dimethyl- (11), 3-isopropyl- (12), and 3,6-diisoproply-1,2-xylylene (13) in acetonitrile (CH 3 CN) were studied by stopped-flow UV-visible spectroscopy. Fluoride ion induced 1,2-elimination from 2-elimination from 2-trimethylsilylbenzocyclobutenyl-1 mesylate (26) was used to generate the reactive molecule benzocyclobutadiene (1') in CD 3 CN, which was observed by flow 1 H NMR spectroscopy at room temperature. The 1 H NMR spectrum (in CD 3 CN) of 1,2-dimethylene-1,2-dihydrothiophene (1 double-prime), obtained by fluoride ion induced 1,4-elimination from 3-(trimethylammoniummethyl)-2-(trimethylsilylmethyl)thiophene iodine was observed by flow 1 H NMR spectroscopy at room temperature. The dimerization rate of 1 double-prime in CH 3 CN, generated in the same manner, was measured by UV-visible spectroscopy. 166 refs., 7 figs., 7 tabs

Abnormal Cerebrovascular Reactivity in Patients with Parkinson’s Disease

Directory of Open Access Journals (Sweden)

Carlos Henrique Ferreira Camargo

2015-01-01

Full Text Available Background. Orthostatic hypotension (OH is an important nonmotor manifestation of Parkinson’s disease (PD. Changes in cerebrovascular reactivity may contribute to this manifestation and can be monitored using transcranial Doppler. Objective. To identify possible changes in cerebrovascular reactivity in patients with OH. Methods. Twenty-two individuals were selected and divided into three groups: with and without OH and controls. Transcranial Doppler was used to assess basal mean blood flow velocity, postapnea mean blood flow velocity, percentage increase in mean blood flow velocity, and cerebrovascular reactivity as measured by the breath-holding index. Results. PD patients had lower values of basal velocity (p=0.019, postapnea velocity (p=0.0015, percentage increase in velocity (p=0.039, and breath-holding index (p=0.04 than the controls. Patients with OH had higher values of basal velocity (p=0.09 and postapnea velocity (p=0.19 but lower values of percentage increase in velocity (p=0.22 and breath-holding index (p=0.32 than patients without OH. Conclusions. PD patients present with abnormalities in a compensatory mechanism that regulates cerebral blood flow. OH could be an indicator of these abnormalities.

Hybrid Multiscale Finite Volume method for multiresolution simulations of flow and reactive transport in porous media

Science.gov (United States)

Barajas-Solano, D. A.; Tartakovsky, A. M.

2017-12-01

We present a multiresolution method for the numerical simulation of flow and reactive transport in porous, heterogeneous media, based on the hybrid Multiscale Finite Volume (h-MsFV) algorithm. The h-MsFV algorithm allows us to couple high-resolution (fine scale) flow and transport models with lower resolution (coarse) models to locally refine both spatial resolution and transport models. The fine scale problem is decomposed into various "local'' problems solved independently in parallel and coordinated via a "global'' problem. This global problem is then coupled with the coarse model to strictly ensure domain-wide coarse-scale mass conservation. The proposed method provides an alternative to adaptive mesh refinement (AMR), due to its capacity to rapidly refine spatial resolution beyond what's possible with state-of-the-art AMR techniques, and the capability to locally swap transport models. We illustrate our method by applying it to groundwater flow and reactive transport of multiple species.

Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry

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Luis R. Domingo

2016-09-01

Full Text Available A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT, is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT, the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

Continuum-Kinetic Hybrid Framework for Chemically Reacting Flows

Data.gov (United States)

National Aeronautics and Space Administration — Predictive modeling of chemically reacting flows is essential for the design and optimization of future hypersonic vehicles. During atmospheric re-entry, complex...

THC-MP: High performance numerical simulation of reactive transport and multiphase flow in porous media

Science.gov (United States)

Wei, Xiaohui; Li, Weishan; Tian, Hailong; Li, Hongliang; Xu, Haixiao; Xu, Tianfu

2015-07-01

The numerical simulation of multiphase flow and reactive transport in the porous media on complex subsurface problem is a computationally intensive application. To meet the increasingly computational requirements, this paper presents a parallel computing method and architecture. Derived from TOUGHREACT that is a well-established code for simulating subsurface multi-phase flow and reactive transport problems, we developed a high performance computing THC-MP based on massive parallel computer, which extends greatly on the computational capability for the original code. The domain decomposition method was applied to the coupled numerical computing procedure in the THC-MP. We designed the distributed data structure, implemented the data initialization and exchange between the computing nodes and the core solving module using the hybrid parallel iterative and direct solver. Numerical accuracy of the THC-MP was verified through a CO2 injection-induced reactive transport problem by comparing the results obtained from the parallel computing and sequential computing (original code). Execution efficiency and code scalability were examined through field scale carbon sequestration applications on the multicore cluster. The results demonstrate successfully the enhanced performance using the THC-MP on parallel computing facilities.

The reactive solid-gas flow of a fluidized bed for UO2 conversion

International Nuclear Information System (INIS)

Juanico, L.E.

1991-01-01

The reactive solid-gas flow of a fluidized bed for UO 2 conversion was modeled. The sedimentation-reaction process was treated using the drift-flux equations. Also, the associated pressure transient due to the reaction gas release was analyzed. An experiment was carried out to compare the results, and pressure transient was numerically simulated, reaching interesting conclusions. (Author) [es

Quantum mechanical tunneling in chemical physics

CERN Document Server

Nakamura, Hiroki

2016-01-01

Quantum mechanical tunneling plays important roles in a wide range of natural sciences, from nuclear and solid-state physics to proton transfer and chemical reactions in chemistry and biology. Responding to the need for further understanding of multidimensional tunneling, the authors have recently developed practical methods that can be applied to multidimensional systems. Quantum Mechanical Tunneling in Chemical Physics presents basic theories, as well as original ones developed by the authors. It also provides methodologies and numerical applications to real molecular systems. The book offers information so readers can understand the basic concepts and dynamics of multidimensional tunneling phenomena and use the described methods for various molecular spectroscopy and chemical dynamics problems. The text focuses on three tunneling phenomena: (1) energy splitting, or tunneling splitting, in symmetric double well potential, (2) decay of metastable state through tunneling, and (3) tunneling effects in chemical...

How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

Directory of Open Access Journals (Sweden)

M. J. Prather

2018-05-01

Full Text Available We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25–30 % of the total reactivities, but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this

Electron beam processing of rubber wood fibers - polypropylene composites. Effects of reactive additives on the physical and mechanical properties

International Nuclear Information System (INIS)

Nor Yuziah Mohd Yunus; Jalaluddin Harun; Khairul Zaman

2000-01-01

The purpose of this study is to determine the suitability of producing agro-fiber reinforced plastic composite (agro-FRPC) from rubber wood fiber blended in polypropylene matrix. The effects of varying fiber dimension and fiber content on the physical and mechanical properties of the composite were evaluated to provide an insight into the fiber matrix adhesion. The effects of reactive additives on the physical and mechanical properties of the composite were evaluated which provides the insight on the reinforcement of the composite. Rubber wood fiber used in this study is currently being used in the manufacturing of medium density fiber (MDF) board. Two sizes of rubber wood fiber were used i.e. 0.5-1.0 mm and 1.0-2.0 mm. Homopolymer polypropylene of MFI 14.0 was used as a matrix. The irradiation work was carried out using electron beam accelerator, 3.0 MeV, 3.0 mA. Various types of reactive additives (RA) with mono-functional, di-functional, tri-functional and oligomer were applied in the blend. For comparison, a conventional chemical cross-linking using two types of maleated polypropylene, MPA (Mw=9,000) and PMAP (Mw=220,000) were also performed. (author)

Electron beam processing of rubber wood fibers - polypropylene composites. Effects of reactive additives on the physical and mechanical properties

Energy Technology Data Exchange (ETDEWEB)

Nor Yuziah Mohd Yunus; Jalaluddin Harun [Universiti Putra Malaysia, Selangor Darul Ehsan (Malaysia); Khairul Zaman [Malaysian Institute for Nuclear Technology Research (MINT), Selangor Darul Ehsan (Malaysia)

2000-07-01

The purpose of this study is to determine the suitability of producing agro-fiber reinforced plastic composite (agro-FRPC) from rubber wood fiber blended in polypropylene matrix. The effects of varying fiber dimension and fiber content on the physical and mechanical properties of the composite were evaluated to provide an insight into the fiber matrix adhesion. The effects of reactive additives on the physical and mechanical properties of the composite were evaluated which provides the insight on the reinforcement of the composite. Rubber wood fiber used in this study is currently being used in the manufacturing of medium density fiber (MDF) board. Two sizes of rubber wood fiber were used i.e. 0.5-1.0 mm and 1.0-2.0 mm. Homopolymer polypropylene of MFI 14.0 was used as a matrix. The irradiation work was carried out using electron beam accelerator, 3.0 MeV, 3.0 mA. Various types of reactive additives (RA) with mono-functional, di-functional, tri-functional and oligomer were applied in the blend. For comparison, a conventional chemical cross-linking using two types of maleated polypropylene, MPA (Mw=9,000) and PMAP (Mw=220,000) were also performed. (author)

Flow-Injection Responses of Diffusion Processes and Chemical Reactions

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov

2000-01-01

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

Core dynamics analysis for reactivity insertion and loss of coolant flow tests using the HTTR

International Nuclear Information System (INIS)

Takamatsu, Kuniyoshi; Nakagawa, Shigeaki; Takeda, Tetsuaki

2007-01-01

The High Temperature engineering Test Reactor (HTTR) is a graphite-moderated and a gas-cooled reactor with a thermal power of 30 MW and a reactor outlet coolant temperature of 950degC (SAITO, 1994). Safety demonstration tests using the HTTR are in progress to verify its inherent safety features and improve the safety technology and design methodology for High-Temperature Gas-cooled Reactors (HTGRs) (TACHIBANA 2002) (NAKAGAWA 2004). The reactivity insertion test is one of the safety demonstration tests for the HTTR. This test simulates the rapid increase in the reactor power by withdrawing the control rod without operating the reactor power control system. In addition, the loss of coolant flow tests has been conducted to simulate the rapid decrease in the reactor power by tripping one, two or all out of three gas circulators. The experimental results have revealed the inherent safety features of HTGRs, such as the negative reactivity feedback effect. The numerical analysis code, which was named ACCORD (TAKAMATSU 2006), was developed to analyze the reactor dynamics including the flow behavior in the HTTR core. We used a conventional method, namely, a one-dimensional flow channel model and reactor kinetics model with a single temperature coefficient, taking into account the temperature changes in the core. However, a slight difference between the analytical and experimental results was observed. Therefore, we have modified this code to use a model with four parallel channels and twenty temperature coefficients in the core. Furthermore, we added another analytical model of the core for calculating the heat conduction between the fuel channels and the core in the case of the loss of coolant flow tests. This paper describes the validation results for the newly developed code using the experimental results of the reactivity insertion test as well as the loss of coolant flow tests by tripping one or two out of three gas circulators. Finally, the pre-analytical result of

Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

Directory of Open Access Journals (Sweden)

T. F. Lyon

Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C₁ through C₁₇, CO, CO₂, NO, NO_x, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

Science.gov (United States)

Xin, Hongliang; Linic, Suljo

2016-06-01

Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

Application of laser diagnostics to sodium-water chemical reaction field

International Nuclear Information System (INIS)

Deguchi, Yoshihiro; Tamura, Kenta; Muranaka, Ryota; Kusano, Koji; Kikuchi, Shin; Kurihara, Akikazu

2013-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes in a steam generator. Therefore the study on sodium-water chemical reactions is of paramount importance for safety reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. The sodium-water counter-flow reactions were measured using laser diagnostics such as laser induced fluorescence, CARS, Raman scattering and photo-fragmentation. The measurement results show that the sodium-water reaction proceeds mainly by the reaction Na + H 2 O → NaOH + H and the main product is NaOH in this reaction. Its forward and backward reaction rates tend to balance with each other and the whole reaction rate reduces as temperature increases. (author)

Experimental determination of sorption in fractured flow systems

Science.gov (United States)

Zimmerman, Mitchell D.; Bennett, Philip C.; Sharp, John M.; Choi, Wan-Joo

2002-09-01

Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated ˜2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.

Plasma-enhanced chemical vapor deposited silicon oxynitride films for optical waveguide bridges for use in mechanical sensors

DEFF Research Database (Denmark)

Storgaard-Larsen, Torben; Leistiko, Otto

1997-01-01

In this paper the influence of RF power, ammonia flow, annealing temperature, and annealing time on the optical and mechanical properties of plasma-enhanced chemically vapor deposited silicon oxynitride films, is presented. A low refractive index (1.47 to 1.48) film having tensile stress has been...

Simplified Thermo-Chemical Modelling For Hypersonic Flow

Science.gov (United States)

Sancho, Jorge; Alvarez, Paula; Gonzalez, Ezequiel; Rodriguez, Manuel

2011-05-01

Hypersonic flows are connected with high temperatures, generally associated with strong shock waves that appear in such flows. At high temperatures vibrational degrees of freedom of the molecules may become excited, the molecules may dissociate into atoms, the molecules or free atoms may ionize, and molecular or ionic species, unimportant at lower temperatures, may be formed. In order to take into account these effects, a chemical model is needed, but this model should be simplified in order to be handled by a CFD code, but with a sufficient precision to take into account the physics more important. This work is related to a chemical non-equilibrium model validation, implemented into a commercial CFD code, in order to obtain the flow field around bodies in hypersonic flow. The selected non-equilibrium model is composed of seven species and six direct reactions together with their inverse. The commercial CFD code where the non- equilibrium model has been implemented is FLUENT. For the validation, the X38/Sphynx Mach 20 case is rebuilt on a reduced geometry, including the 1/3 Lref forebody. This case has been run in laminar regime, non catalytic wall and with radiative equilibrium wall temperature. The validated non-equilibrium model is applied to the EXPERT (European Experimental Re-entry Test-bed) vehicle at a specified trajectory point (Mach number 14). This case has been run also in laminar regime, non catalytic wall and with radiative equilibrium wall temperature.

Hydrogen fluoride (HF) substance flow analysis for safe and sustainable chemical industry.

Science.gov (United States)

Kim, Junbeum; Hwang, Yongwoo; Yoo, Mijin; Chen, Sha; Lee, Ik-Mo

2017-11-01

In this study, the chemical substance flow of hydrogen fluoride (hydrofluoric acid, HF) in domestic chemical industries in 2014 was analyzed in order to provide a basic material and information for the establishment of organized management system to ensure safety during HF applications. A total of 44,751 tons of HF was made by four domestic companies (in 2014); import amount was 95,984 tons in 2014 while 21,579 tons of HF was imported in 2005. The export amount of HF was 2180 tons, of which 2074 ton (China, 1422 tons, U.S. 524 tons, and Malaysia, 128 tons) was exported for the manufacturing of semiconductors. Based on the export and import amounts, it can be inferred that HF was used for manufacturing semiconductors. The industries applications of 161,123 tons of HF were as follows: manufacturing of basic inorganic chemical substance (27,937 tons), manufacturing of other chemical products such as detergents (28,208 tons), manufacturing of flat display (24,896 tons), and manufacturing of glass container package (22,002 tons). In this study, an analysis of the chemical substance flow showed that HF was mainly used in the semiconductor industry as well as glass container manufacturing. Combined with other risk management tools and approaches in the chemical industry, the chemical substance flow analysis (CSFA) can be a useful tool and method for assessment and management. The current CSFA results provide useful information for policy making in the chemical industry and national systems. Graphical abstract Hydrogen fluoride chemical substance flows in 2014 in South Korea.

Experimental and numerical reaction analysis on sodium-water chemical reaction field

International Nuclear Information System (INIS)

Deguchi, Yoshihiro; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2015-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using an elementary reaction analysis. A quasi one-dimensional flame model is applied to a sodium-water counter-flow reaction field. The analysis contains 25 elementary reactions, which consist of 17 H_2-O_2 and 8 Na-H_2O reactions. Temperature and species concentrations in the counter-flow reaction field were measured using laser diagnostics such as LIF and CARS. The main reaction in the experimental conditions is Na+H_2O → NaOH+H and OH is produced by H_2O+H → H_2+OH. It is demonstrated that the reaction model in this study well explains the structure of the sodium-water counter-flow diffusion flame. (author)

Analysis of the trend to equilibrium of a chemically reacting system

International Nuclear Information System (INIS)

Kremer, Gilberto M; Bianchi, Miriam Pandolfi; Soares, Ana Jacinta

2007-01-01

In this present paper, a quaternary gaseous reactive mixture, for which the chemical reaction is close to its final stage and the elastic and reactive frequencies are comparable, is modelled within the Boltzmann equation extended to reacting gases. The main objective is a detailed analysis of the non-equilibrium effects arising in the reactive system A 1 + A 2 ↔ A 3 + A 4 , in a flow regime which is considered not far away from thermal, mechanical and chemical equilibrium. A first-order perturbation solution technique is applied to the macroscopic field equations for the spatially homogeneous gas system, and the trend to equilibrium is studied in detail. Adopting elastic hard-spheres and reactive line-of-centres cross sections and an appropriate choice of the input distribution functions-which allows us to distinguish the two cases where the constituents are either at same or different temperatures-explicit computations of the linearized production terms for mass, momentum and total energy are performed for each gas species. The departures from the equilibrium states of densities, temperatures and diffusion fluxes are characterized by small perturbations of their corresponding equilibrium values. For the hydrogen-chlorine system, the perturbations are plotted as functions of time for both cases where the species are either at the same or different temperatures. Moreover, the trend to equilibrium of the reaction rates is represented for the forward and backward reaction H 2 + Cl ↔ HCl + H

Synthesis of functional nanocrystallites through reactive thermal plasma processing

Directory of Open Access Journals (Sweden)

Takamasa Ishigaki and Ji-Guang Li

2007-01-01

Full Text Available A method of synthesizing functional nanostructured powders through reactive thermal plasma processing has been developed. The synthesis of nanosized titanium oxide powders was performed by the oxidation of solid and liquid precursors. Quench gases, either injected from the shoulder of the reactor or injected counter to the plasma plume from the bottom of the reactor, were used to vary the quench rate, and therefore the particle size, of the resultant powders. The experimental results are well supported by numerical analysis on the effects of the quench gas on the flow pattern and temperature field of the thermal plasma as well as on the trajectory and temperature history of the particles. The plasma-synthesized TiO2 nanoparticles showed phase preferences different from those synthesized by conventional wet-chemical processes. Nanosized particles of high crystallinity and nonequilibrium chemical composition were formed in one step via reactive thermal plasma processing.

Coupled hydrogeological and reactive transport modelling of the Simpevarp area (Sweden)

International Nuclear Information System (INIS)

Molinero, Jorge; Raposo, Juan R.; Galindez, Juan M.; Arcos, David; Guimera, Jordi

2008-01-01

The Simpevarp area is one of the alternative sites being considered for the deep geological disposal of high level radioactive waste in Sweden. In this paper, a coupled regional groundwater flow and reactive solute transport model of the Simpevarp area is presented that integrates current hydrogeological and hydrochemical data of the area. The model simulates the current hydrochemical pattern of the groundwater system in the area. To that aim, a conceptual hydrochemical model was developed in order to represent the dominant chemical processes. Groundwater flow conditions were reproduced by taking into account fluid-density-dependent groundwater flow and regional hydrogeologic boundary conditions. Reactive solute transport calculations were performed on the basis of the velocity field so obtained. The model was calibrated and sensitivity analyses were carried out in order to investigate the effects of heterogeneities of hydraulic conductivity in the subsurface medium. Results provided by the reactive transport model are in good agreement with much of the measured hydrochemical data. This paper emphasizes the appropriateness of the use of reactive solute transport models when water-rock interaction reactions are involved, and demonstrates what powerful tools they are for the interpretation of hydrogeological and hydrochemical data from site geological repository characterization programs, by providing a qualitative framework for data analysis and testing of conceptual assumptions in a process-oriented approach

Effect of reactive and un-reactive substrates on photopolymerization of self-etching adhesives with different aggressiveness.

Science.gov (United States)

Zhang, Ying; Wang, Yong

2013-01-01

The study investigated the influence of reactive (enamel) and un-reactive (glass) substrates on photo-polymerization of self-etching adhesives. Two commercial adhesives Adper Prompt L-Pop (APLP, pH~0.8) and Adper Easy Bond (AEB, pH~2.5) were applied onto prepared enamel and glass substrates using the same protocol. Micro-Raman spectroscopy was employed to determine the degree of conversion (DC) and the involved mechanism. DC of APLP was dramatically enhanced from ~9.4% to ~82.0% as when changing from glass to enamel, while DC of AEB on both substrates showed no difference. The DC distributions along the adhesive layers of the APLP and AEB on enamel showed descending and constant trends, respectively. Spectral analysis disclosed that the difference in chemical reaction of the two adhesives with enamel might be associated with the results. The chemical reaction of the adhesives with enamel significantly improved the DC of the strong APLP, but not that of the mild AEB.

Unsteady Flow of Reactive Viscous, Heat Generating/Absorbing Fluid with Soret and Variable Thermal Conductivity

Directory of Open Access Journals (Sweden)

I. J. Uwanta

2014-01-01

Full Text Available This study investigates the unsteady natural convection and mass transfer flow of viscous reactive, heat generating/absorbing fluid in a vertical channel formed by two infinite parallel porous plates having temperature dependent thermal conductivity. The motion of the fluid is induced due to natural convection caused by the reactive property as well as the heat generating/absorbing nature of the fluid. The solutions for unsteady state temperature, concentration, and velocity fields are obtained using semi-implicit finite difference schemes. Perturbation techniques are used to get steady state expressions of velocity, concentration, temperature, skin friction, Nusselt number, and Sherwood number. The effects of various flow parameters such as suction/injection (γ, heat source/sinks (S, Soret number (Sr, variable thermal conductivity δ, Frank-Kamenetskii parameter λ, Prandtl number (Pr, and nondimensional time t on the dynamics are analyzed. The skin friction, heat transfer coefficients, and Sherwood number are graphically presented for a range of values of the said parameters.

Quantum indistinguishability in chemical reactions.

Science.gov (United States)

Fisher, Matthew P A; Radzihovsky, Leo

2018-05-15

Quantum indistinguishability plays a crucial role in many low-energy physical phenomena, from quantum fluids to molecular spectroscopy. It is, however, typically ignored in most high-temperature processes, particularly for ionic coordinates, implicitly assumed to be distinguishable, incoherent, and thus well approximated classically. We explore enzymatic chemical reactions involving small symmetric molecules and argue that in many situations a full quantum treatment of collective nuclear degrees of freedom is essential. Supported by several physical arguments, we conjecture a "quantum dynamical selection" (QDS) rule for small symmetric molecules that precludes chemical processes that involve direct transitions from orbitally nonsymmetric molecular states. As we propose and discuss, the implications of the QDS rule include ( i ) a differential chemical reactivity of para- and orthohydrogen, ( ii ) a mechanism for inducing intermolecular quantum entanglement of nuclear spins, ( iii ) a mass-independent isotope fractionation mechanism, ( iv ) an explanation of the enhanced chemical activity of "reactive oxygen species", ( v ) illuminating the importance of ortho-water molecules in modulating the quantum dynamics of liquid water, and ( vi ) providing the critical quantum-to-biochemical linkage in the nuclear spin model of the (putative) quantum brain, among others.

Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D

Science.gov (United States)

Bailey, Ryan T.; Morway, Eric D.; Niswonger, Richard G.; Gates, Timothy K.

2013-01-01

A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

Measurements of total OH reactivity during PROPHET-AMOS 2016

Science.gov (United States)

Rickly, P.; Sakowski, J.; Bottorff, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Locoge, N.; Dusanter, S.

2017-12-01

As one of the main oxidant in the atmosphere, the hydroxyl radical (OH) initiates the oxidation of volatile organic compounds that can lead to the formation of ozone and secondary organic aerosols. Understanding both the sources and sinks of OH is therefore important to address issues related to air quality and climate change. Measurements of total OH reactivity can provide an important test of our understanding of the OH radical budget. Recent measurements of total reactivity in many environments have been greater than calculated based on the measured concentration of VOCs, suggesting that important OH sinks in these environments are not well characterized. Measurements of total OH reactivity were performed in a forested environment during the PROPHET - AMOS field campaign (Program for Research on Oxidants: PHotochemisty, Emissions, and Transport - Atmospheric Measurements of Oxidants in Summer) using the Comparative Reactivity Method (CRM) and the Total OH Loss Rate Method (TOHLM). The site is characterized by large emissions of isoprene and monoterpenes and low anthropogenic influence. Measurements of total OH reactivity using these two techniques agree to within their respective uncertainties, giving confidence in the measured OH reactivity. In addition, measurements of trace gases (VOCs, NOx, O3) were used to perform a comprehensive apportionment of OH sinks. These measurements are used in a chemical model using the Master Chemical Mechanism to calculate the expected OH reactivity. The results will be compared to previous measurements of total OH reactivity at this site.

Mechanisms of Reactive Stroma-Induced Tumorigenesis in Prostate Cancer

Science.gov (United States)

2016-11-01

type I receptor blocker (SI Appendix, Fig. S9). Together, these results further support the concept that TGF-β1–expressing prostate cancer cells induce...of NBT-II bladder carcinoma cells to condi- tioned medium from normal fetal urogenital sinus. Cancer Res 47(11):2955–2960. 22. Nimmo R, Woollard A...AWARD NUMBER: W81XWH-12-1-0197 TITLE: Mechanisms of Reactive Stroma - Induced Tumorigenesis in Prostate Cancer PRINCIPAL INVESTIGATOR

Enhancing Reactivity in Structural Energetic Materials

Science.gov (United States)

Glumac, Nick

2017-06-01

In many structural energetic materials, only a small fraction of the metal oxidizes, and yet this provides a significant boost in the overall energy release of the system. Different methodologies to enhance this reactivity include alloying and geometric modifications of microstructure of the reactive material (RM). In this presentation, we present the results of several years of systematic study of both chemical (alloy) and mechanical (geometry) effects on reactivity for systems with typical charge to case mass ratios. Alloys of aluminum with magnesium and lithium are considered, as these are common alloys in aerospace applications. In terms of geometric modifications, we consider surface texturing, inclusion of dense additives, and inclusion of voids. In all modifications, a measurable influence on output is observed, and this influence is related to the fragment size distribution measured from the observed residue. Support from DTRA is gratefully acknowledged.

Reactive transport models and simulation with ALLIANCES

International Nuclear Information System (INIS)

Leterrier, N.; Deville, E.; Bary, B.; Trotignon, L.; Hedde, T.; Cochepin, B.; Stora, E.

2009-01-01

Many chemical processes influence the evolution of nuclear waste storage. As a result, simulations based only upon transport and hydraulic processes fail to describe adequately some industrial scenarios. We need to take into account complex chemical models (mass action laws, kinetics...) which are highly non-linear. In order to simulate the coupling of these chemical reactions with transport, we use a classical Sequential Iterative Approach (SIA), with a fixed point algorithm, within the mainframe of the ALLIANCES platform. This approach allows us to use the various transport and chemical modules available in ALLIANCES, via an operator-splitting method based upon the structure of the chemical system. We present five different applications of reactive transport simulations in the context of nuclear waste storage: 1. A 2D simulation of the lixiviation by rain water of an underground polluted zone high in uranium oxide; 2. The degradation of the steel envelope of a package in contact with clay. Corrosion of the steel creates corrosion products and the altered package becomes a porous medium. We follow the degradation front through kinetic reactions and the coupling with transport; 3. The degradation of a cement-based material by the injection of an aqueous solution of zinc and sulphate ions. In addition to the reactive transport coupling, we take into account in this case the hydraulic retroaction of the porosity variation on the Darcy velocity; 4. The decalcification of a concrete beam in an underground storage structure. In this case, in addition to the reactive transport simulation, we take into account the interaction between chemical degradation and the mechanical forces (cracks...), and the retroactive influence on the structure changes on transport; 5. The degradation of the steel envelope of a package in contact with a clay material under a temperature gradient. In this case the reactive transport simulation is entirely directed by the temperature changes and

Water Susceptibility and Mechanical Properties of Thermoplastic Starch–Pectin Blends Reactively Extruded with Edible Citric Acid

OpenAIRE

Da Róz,Alessandra Luzia; Veiga-Santos,Pricila; Ferreira,Adriane Medeiros; Antunes,Thaís Cristina Ribeiro; Leite,Fabio de Lima; Yamaji,Fabio Minoru; Carvalho,Antonio José Felix de

2016-01-01

Pectin and starch are edible, non-toxic, biodegradable and obtained from renewable sources. Also, have the benefit to be easily cross-linked producing hydrogels. Reactive extrusion with edible citric acid and cross linking interactions was evaluated on extruded thermoplastic in natura and cationic starch-pectin blends. Materials water susceptibility and mechanical properties were characterised. Reactive extrusion decreased (up to 75% in natura starch) mechanical properties. Also have decrease...

Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

Science.gov (United States)

Lee, Seung-Mahn

2003-10-01

Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP

Investigation of air gasification of micronized coal, mechanically activated using the plasma control of the process

Directory of Open Access Journals (Sweden)

Butakov Evgenii

2017-01-01

Full Text Available Combination of the processes of coal combustion and gasification into a single technology of mechano-chemical and plasma-chemical activation is of a considerable scientific and technological interest. Enhancement of coal reactivity at their grinding with mechanical activation is associated with an increase in the reaction rate of carbon material, and at plasma-chemical effect, the main is an increase in reactivity of the oxidizing agent caused by the high plasma temperatures of atomic oxygen. The process of gasification was studied on the 1-MW setup with tangential scroll supply of pulverized coal-air mixture and cylindrical reaction chamber. Coal ground by the standard boiler mill is fed to the disintegrator, then, it is sent to the scroll inlet of the burner-reactor with the transport air. Pulverized coal is ignited by the plasmatron of 10-kW power. In experiments on air gasification of micronized coal, carried out at the temperature in the reaction chamber of 1000-1200°C and air excess α = 0.3-1, the data on CO concentration of 11% and H2 concentration of up to 6% were obtained. Air and air-steam gasification of mechanically-activated micronized coals with plasma control was calculated using SigmaFlow software package.

Investigation of air gasification of micronized coal, mechanically activated using the plasma control of the process

Science.gov (United States)

Butakov, Evgenii; Burdukov, Anatoly; Chernetskiy, Mikhail; Kuznetsov, Victor

2017-10-01

Combination of the processes of coal combustion and gasification into a single technology of mechano-chemical and plasma-chemical activation is of a considerable scientific and technological interest. Enhancement of coal reactivity at their grinding with mechanical activation is associated with an increase in the reaction rate of carbon material, and at plasma-chemical effect, the main is an increase in reactivity of the oxidizing agent caused by the high plasma temperatures of atomic oxygen. The process of gasification was studied on the 1-MW setup with tangential scroll supply of pulverized coal-air mixture and cylindrical reaction chamber. Coal ground by the standard boiler mill is fed to the disintegrator, then, it is sent to the scroll inlet of the burner-reactor with the transport air. Pulverized coal is ignited by the plasmatron of 10-kW power. In experiments on air gasification of micronized coal, carried out at the temperature in the reaction chamber of 1000-1200°C and air excess α = 0.3-1, the data on CO concentration of 11% and H2 concentration of up to 6% were obtained. Air and air-steam gasification of mechanically-activated micronized coals with plasma control was calculated using SigmaFlow software package.

High Pressure Combustion Experimental Facility(HPCEF) for Studies on Combustion in Reactive Flows

Science.gov (United States)

2017-12-13

SECURITY CLASSIFICATION OF: 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND SUBTITLE 13. SUPPLEMENTARY NOTES 12. DISTRIBUTION AVAILIBILITY STATEMENT 6...Report: High Pressure Combustion Experimental Facility (HPCEF) for Studies on Combustion in Reactive Flows The views, opinions and/or findings... contained in this report are those of the author(s) and should not contrued as an official Department of the Army position, policy or decision, unless so

The Simplest Flowchart Stating the Mechanisms for Organic Xenobiotics-induced Toxicity: Can it Possibly be Accepted as a "Central Dogma" for Toxic Mechanisms?

Science.gov (United States)

Park, Yeong-Chul; Lee, Sundong; Cho, Myung-Haing

2014-09-01

Xenobiotics causing a variety of toxicity in biological systems could be classified as two types, inorganic and organic chemicals. It is estimated that the organic xenobiotics are responsible for approximately 80~90% of chemical-induced toxicity in human population. In the class for toxicology, we have encountered some difficulties in explaining the mechanisms of toxicity caused especially by organic chemicals. Here, a simple flowchart was introduced for explaining the mechanism of toxicity caused by organic xenobiotics, as the central dogma of molecular biology. This flowchart, referred to as a central dogma, was described based on a view of various aspects as follows: direct-acting chemicals vs. indirect-acting chemicals, cytochrome P450-dependent vs. cytochrome P450-independent biotransformation, reactive intermediates, reactivation, toxicokinetics vs. toxicodynamics, and reversibility vs. irreversibility. Thus, the primary objective of this flowchart is to help better understanding of the organic xenobiotics-induced toxic mechanisms, providing a major pathway for toxicity occurring in biological systems.

Mechanisms and predictions for subcooled flow boiling CHF

International Nuclear Information System (INIS)

Liu, Wei; Nariai, Hideki; Inasaka, Fujio

2000-01-01

Corresponding to the two kinds of flow pattern reported in literature for subcooled flow boiling, two kinds of CHF triggering mechanism are considered existing with working in different working scope. On the base of a criterion proposed recently by the present authors, subcooled flow boiling data firstly are categorized into two groups by judging whether the first kind or the second kind of flow pattern is established. Possible CHF triggering mechanisms and prediction methods for the two kinds of flow pattern condition are discussed. By considering both the flow pattern development and CHF triggering mechanism, a detailed data categorization is carried out. The corresponding CHF occurrence properties in different data groups are summarized. Parametric trends are reviewed for the first and second kind of data group working condition respectively. Mass flux, pressure, inlet subcooling and inner diameter show almost same effects in the two different working conditions, while the ratio of heated length to diameter's effects on CHF show to be different. Research for the L/D effect on the CHF transverse the interface of the different data groups is carried out. (author)

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

Science.gov (United States)

Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

2016-06-01

Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

Quantum mechanical algebraic variational methods for inelastic and reactive molecular collisions

Science.gov (United States)

Schwenke, David W.; Haug, Kenneth; Zhao, Meishan; Truhlar, Donald G.; Sun, Yan

1988-01-01

The quantum mechanical problem of reactive or nonreactive scattering of atoms and molecules is formulated in terms of square-integrable basis sets with variational expressions for the reactance matrix. Several formulations involving expansions of the wave function (the Schwinger variational principle) or amplitude density (a generalization of the Newton variational principle), single-channel or multichannel distortion potentials, and primitive or contracted basis functions are presented and tested. The test results, for inelastic and reactive atom-diatom collisions, suggest that the methods may be useful for a variety of collision calculations and may allow the accurate quantal treatment of systems for which other available methods would be prohibitively expensive.

Molecular mechanisms for the destabilization and restabilization of reactivated spatial memory in the Morris water maze

Directory of Open Access Journals (Sweden)

Kim Ryang

2011-02-01

Full Text Available Abstract Background Memory retrieval is not a passive process. Recent studies have shown that reactivated memory is destabilized and then restabilized through gene expression-dependent reconsolidation. Molecular studies on the regulation of memory stability after retrieval have focused almost exclusively on fear memory, especially on the restabilization process of the reactivated fear memory. We previously showed that, similarly with fear memories, reactivated spatial memory undergoes reconsolidation in the Morris water maze. However, the underlying molecular mechanisms by which reactivated spatial memory is destabilized and restabilized remain poorly understood. In this study, we investigated the molecular mechanism that regulates the stability of the reactivated spatial memory. Results We first showed that pharmacological inactivation of the N-methyl-D-aspartate glutamate receptor (NMDAR in the hippocampus or genetic inhibition of cAMP-responsible element binding protein (CREB-mediated transcription disrupted reactivated spatial memory. Finally, we showed that pharmacological inhibition of cannabinoid receptor 1 (CB1 and L-type voltage gated calcium channels (LVGCCs in the hippocampus blocked the disruption of the reactivated spatial memory by the inhibition of protein synthesis. Conclusions Our findings indicated that the reactivated spatial memory is destabilized through the activation of CB1 and LVGCCs and then restabilized through the activation of NMDAR- and CREB-mediated transcription. We also suggest that the reactivated spatial memory undergoes destabilization and restabilization in the hippocampus, through similar molecular processes as those for reactivated contextual fear memories, which require CB1 and LVGCCs for destabilization and NMDAR and CREB for restabilization.

Evaluation of a high-throughput peptide reactivity format assay for assessment of the skin sensitization potential of chemicals

Directory of Open Access Journals (Sweden)

Chin Lin eWong

2016-03-01

Full Text Available The direct peptide reactivity assay (DPRA is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium and high concentrations and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme and non-sensitizers with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF, cysteine- (Ac-RFAACAA and lysine- (Ac-RFAAKAA containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7% and glass (47.3% vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2,4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further

Large-eddy simulation of pollutant dispersion from a ground-level area source over urban street canyons with irreversible chemical reactions

Science.gov (United States)

Du, T. Z.; Liu, C.-H.; Zhao, Y. B.

2014-10-01

In this study, the dispersion of chemically reactive pollutants is calculated by large-eddy simulation (LES) in a neutrally stratified urban canopy layer (UCL) over urban areas. As a pilot attempt, idealized street canyons of unity building-height-to-street-width (aspect) ratio are used. Nitric oxide (NO) is emitted from the ground surface of the first street canyon into the domain doped with ozone (O3). In the absence of ultraviolet radiation, this irreversible chemistry produces nitrogen dioxide (NO2), developing a reactive plume over the rough urban surface. A range of timescales of turbulence and chemistry are utilized to examine the mechanism of turbulent mixing and chemical reactions in the UCL. The Damköhler number (Da) and the reaction rate (r) are analyzed along the vertical direction on the plane normal to the prevailing flow at 10 m after the source. The maximum reaction rate peaks at an elevation where Damköhler number Da is equal or close to unity. Hence, comparable timescales of turbulence and reaction could enhance the chemical reactions in the plume.

Passivation of mechanically polished, chemically etched and anodized zirconium in various aqueous solutions: Impedance measurements

International Nuclear Information System (INIS)

Abo-Elenien, G.M.; Abdel-Salam, O.E.

1987-01-01

Zirconium and its alloys are finding increasing applications especially in water-cooled nuclear reactors. Because of the fact that zirconium is electronegative (E 0 = -1.529V) its corrosion resistance in aqueous solutions is largely determined by the existence of a thin oxide film on its surface. The structure and properties of this film depend in the first place on the method of surface pre-treatment. This paper presents an experimental study of the nature of the oxide film on mechanically polished, chemically etched and anodized zirconium. Ac impedance measurements carried out in various acidic, neutral and alkaline solutions show that the film thickness depends on the method of surface pre-treatment and the type of electrolyte solution. The variation of the potential and impedance during anodization of zirconium at low current density indicates that the initial stages of polarization consist of oxide build-up at a rate dependent on the nature of the electrode surface and the electrolyte. Oxygen evolution commences at a stage where oxide thickening starts to decline. The effect of frequency on the measured impedance indicates that the surface reactivity, and hence the corrosion rate, decreases in the following order: mechanically polished > chemically etched > anodized

A parametric transfer function methodology for analyzing reactive transport in nonuniform flow.

Science.gov (United States)

Luo, Jian; Cirpka, Olaf A; Fienen, Michael N; Wu, Wei-min; Mehlhorn, Tonia L; Carley, Jack; Jardine, Philip M; Criddle, Craig S; Kitanidis, Peter K

2006-02-01

We analyze reactive transport during in-situ bioremediation in a nonuniform flow field, involving multiple extraction and injection wells, by the method of transfer functions. Gamma distributions are used as parametric models of the transfer functions. Apparent parameters of classical transport models may be estimated from those of the gamma distributions by matching temporal moments. We demonstrate the method by application to measured data taken at a field experiment on bioremediation conducted in a multiple-well system in Oak Ridge, TN. Breakthrough curves (BTCs) of a conservative tracer (bromide) and a reactive compound (ethanol) are measured at multi-level sampling (MLS) wells and in extraction wells. The BTCs of both compounds are jointly analyzed to estimate the first-order degradation rate of ethanol. To quantify the tracer loss, we compare the approaches of using a scaling factor and a first-order decay term. Results show that by including a scaling factor both gamma distributions and inverse-Gaussian distributions (transfer functions according to the advection-dispersion equation) are suitable to approximate the transfer functions and estimate the reactive rate coefficients for both MLS and extraction wells. However, using a first-order decay term for tracer loss fails to describe the BTCs at the extraction well, which is affected by the nonuniform distribution of travel paths.

The Simplest Flowchart Stating the Mechanisms for Organic Xenobiotics-induced Toxicity: Can it Possibly be Accepted as a “Central Dogma” for Toxic Mechanisms?

Science.gov (United States)

Lee, Sundong; Cho, Myung-Haing

2014-01-01

Xenobiotics causing a variety of toxicity in biological systems could be classified as two types, inorganic and organic chemicals. It is estimated that the organic xenobiotics are responsible for approximately 80~90% of chemical-induced toxicity in human population. In the class for toxicology, we have encountered some difficulties in explaining the mechanisms of toxicity caused especially by organic chemicals. Here, a simple flowchart was introduced for explaining the mechanism of toxicity caused by organic xenobiotics, as the central dogma of molecular biology. This flowchart, referred to as a central dogma, was described based on a view of various aspects as follows: direct-acting chemicals vs. indirect-acting chemicals, cytochrome P450-dependent vs. cytochrome P450-independent biotransformation, reactive intermediates, reactivation, toxicokinetics vs. toxicodynamics, and reversibility vs. irreversibility. Thus, the primary objective of this flowchart is to help better understanding of the organic xenobiotics-induced toxic mechanisms, providing a major pathway for toxicity occurring in biological systems. PMID:25343011

Neurocognitive mechanisms of the flow state.

Science.gov (United States)

Harris, David J; Vine, Samuel J; Wilson, Mark R

2017-01-01

While the experience of flow is often described in attentional terms-focused concentration or task absorption-specific cognitive mechanisms have received limited interest. We propose that an attentional explanation provides the best way to advance theoretical models and produce practical applications, as well as providing potential solutions to core issues such as how an objectively difficult task can be subjectively effortless. Recent research has begun to utilize brain-imaging techniques to investigate neurocognitive changes during flow, which enables attentional mechanisms to be understood in greater detail. Some tensions within flow research are discussed; including the dissociation between psychophysiological and experiential measures, and the equivocal neuroimaging findings supporting prominent accounts of hypofrontality. While flow has received only preliminary investigation from a neuroscientific perspective, findings already provide important insights into the crucial role played by higher-order attentional networks, and clear indications of reduced activity in brain regions linked to self-referential processing. The manner in which these processes may benefit sporting performance are discussed. © 2017 Elsevier B.V. All rights reserved.

Soret and Hall effects on unsteady MHD free convection flow of ...

African Journals Online (AJOL)

International Journal of Engineering, Science and Technology ... effects on unsteady MHD free convection flow of radiating and chemically reactive fluid ... Expressions for shear stress, rate of heat transfer and rate of mass transfer at the plate ...

Investigation of Reactivity Feedback Mechanism of Axial and Radial Expansion Effect of Metal-Fueled Sodium-Cooled Fast Reactor

International Nuclear Information System (INIS)

Seong, Seung-Hwan; Choi, Chi-Woong; Jeong, Tae-Kyung; Ha, Gi-Seok

2015-01-01

The major inherent reactivity feedback models for a ceramic fuel used in a conventional light water reactor are Doppler feedback and moderator feedback. The metal fuel has these two reactivity feedback mechanisms previously mentioned. In addition, the metal fuel has two more reactivity feedback models related to the thermal expansion phenomena of the metal fuel. Since the metal fuel has a good capability to expand according to the temperature changes of the core, two more feedback mechanisms exist. These additional two feedback mechanism are important to the inherent safety of metal fuel and can make metal-fueled SFR safer than oxide-fueled SFR. These phenomena have already been applied to safety analysis on design extended condition. In this study, the effect of these characteristics on power control capability was examined through a simple load change operation. The axial expansion mechanism is induced from the change of the fuel temperature according to the change of the power level of PGSFR. When the power increases, the fuel temperatures in the metal fuel will increase and then the reactivity will decrease due to the axial elongation of the metal fuel. To evaluate the expansion effect, 2 cases were simulated with the same scenario by using MMS-LMR code developed at KAERI. The first simulation was to analyze the change of the reactor power according to the change of BOP power without the reactivity feedback model of the axial and radial expansion of the core during the power transient event. That is to say, the core had only two reactivity feedback mechanism of Doppler and coolant temperature

On-chip determination of C-reactive protein using magnetic particles in continuous flow.

Science.gov (United States)

Phurimsak, Chayakom; Tarn, Mark D; Peyman, Sally A; Greenman, John; Pamme, Nicole

2014-11-04

We demonstrate the application of a multilaminar flow platform, in which functionalized magnetic particles are deflected through alternating laminar flow streams of reagents and washing solutions via an external magnet, for the rapid detection of the inflammatory biomarker, C-reactive protein (CRP). The two-step sandwich immunoassay was accomplished in less than 60 s, a vast improvement on the 80-300 min time frame required for enzyme-linked immunosorbent assays (ELISA) and the 50 min necessary for off-chip magnetic particle-based assays. The combination of continuous flow and a stationary magnet enables a degree of autonomy in the system, while a detection limit of 0.87 μg mL(-1) makes it suitable for the determination of CRP concentrations in clinical diagnostics. Its applicability was further proven by assaying real human serum samples and comparing those results to values obtained using standard ELISA tests.

Abiotic pyrite reactivity versus nitrate, selenate and selenite using chemical and electrochemical methods

International Nuclear Information System (INIS)

Ignatiadis, I.; Betelu, S.; Gaucher, E.; Tournassat, C.; Chainet, F.

2010-01-01

Document available in extended abstract form only. This work is part of ReCosy European project (www.recosy.eu), whose main objectives are the sound understanding of redox phenomena controlling the long-term release/retention of radionuclides in nuclear waste disposal and providing tools to apply the results to performance assessment/safety case. Redox is one of the main factor affecting speciation and mobility of redox-sensitive radionuclides. Thus, it is of a great importance to investigate the redox reactivity of the host radioactive waste formations, particularly when exposed to redox perturbations. Callovo-Oxfordian formation (COx), a clay rock known as an anoxic and reducing system, was selected in France as the most suitable location to store nuclear waste. Iron (II) sulfide, mostly constituted of pyrite (FeS 2 ), iron (II) carbonate, iron(II) bearing clays and organic matter are considered to account almost entirely for the total reducing capacity of the rock. We report here the redox reactivity of pyrite upon exposure to nitrate (N(V)), selenate (Se(VI)) and selenite (Se(IV)) that possibly occur in the nuclear storage. Both, chemical and electrochemical kinetic approaches were simultaneously conducted such as to (i) determine the kinetics parameters of the reactions and (ii) understand the kinetic mechanisms. In order to reach similar conditions that are encountered in the storage system, all experiments were realised in NaCl 0.1 M, near neutral pH solutions, and an abiotic glove box (O 2 less than 10 -8 M). Chemical approach has consisted to set in contact pyrite in grains with solutions containing respectively nitrate, selenate and selenite. Reactants and products chemical analyses, conducted at different contact times, allowed us to assess the kinetics of oxidant reduction. Electrochemical approach has consisted in the continuous or semi-continuous analysis of large surface pyrite electrodes immersed in solutions with or without oxidant (nitrate

Nasal hyper-reactivity is a common feature in both allergic and nonallergic rhinitis.

Science.gov (United States)

Segboer, C L; Holland, C T; Reinartz, S M; Terreehorst, I; Gevorgyan, A; Hellings, P W; van Drunen, C M; Fokkens, W J

2013-11-01

Nasal hyper-reactivity is an increased sensitivity of the nasal mucosa to various nonspecific stimuli. Both allergic rhinitis (AR) and nonallergic rhinitis (NAR) patients can elicit nasal hyper-reactivity symptoms. Differences in the prevalence or type of nasal hyper-reactivity in AR and NAR patients are largely unknown. In this study, we quantitatively and qualitatively assessed nasal hyper-reactivity in AR and NAR. In the first part, an analysis of a prospectively collected database was performed to reveal patient-reported symptoms of hyper-reactivity. In the second part, cold dry air provocation (CDA) was performed as a hyper-reactivity measure in AR and NAR patients and healthy controls, and symptoms scores, nasal secretions and peak nasal inspiratory flow were measured. Comparisons were made between AR and NAR patients in both studies. The database analysis revealed high hyper-reactivity prevalence in AR (63.4%) and NAR (66.9%). There were no differences between AR and NAR in terms of the number or type of hyper-reactivity stimuli. Hyper-reactivity to physical stimuli did not exclude a response to chemical stimuli, or vice versa. CDA provocation resulted in a significant increase in rhinitis symptoms and the amount of nasal secretions in AR and NAR patients, but not in controls. We found no quantitative or qualitative differences in nasal hyper-reactivity between AR and NAR patients. It is not possible to differentiate NAR subpopulations based on physical or chemical stimuli. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

An introduction to reactive power compensation for wind farms

Energy Technology Data Exchange (ETDEWEB)

Nigim, K.A. [Waterloo Univ., Ont. (Canada). Dept. of Electrical and Computer Engineering; Cairo Univ., Giza (Egypt). Faculty of Engineering; Zobaa, A.F.; El Amin, I. [King Fahd Univ. of Petroleum and Minerals, Dhahran (Saudi Arabia). Dept. of Electrical Engineering

2005-07-01

The paper summarises the refereed contributions of seven articles reviewed for publication in the IJETP - Special Issue on 'Reactive compensation for wind farms'. The main goal of the special issue is to provide a forum to exchange information on the reactive power compensation requirements for wind farms and introducing possible price mechanisms for today's deregulated power industry. Uncompensated reactive power causes stress on the hosting utility grid as well as added expenses, which create in difficulties for power purchasing agreements from independent wind energy producers. Wind power producers need to comply with the hosting utility grid interconnection standards, e.g., voltage and frequency, as well as to provide controllable active and reactive sources of power. Active power supply is mainly dependent on the potential of wind power produced and the turbine design. Reactive power demand on the other hand depends on the conversion devices and the recovered power quantity fed to the grid. Static Var Compensators (SVC), Unified Power Quality Conditioners (UPQC), Unified Power Flow Controllers (UPFC), and the Distributed Static Synchronous Compensators (DSTATCOM) are all new emerging devices aimed at regulating the reactive power requirements. The excellent controllability of these devices has paved the way to flexible and dynamic controllers that are capable of regulating the flow of active and reactive power components. These devices are now suggested for the control of the reactive power requirement of wind generators. Studies have demonstrated acceptable voltage stabilisation results. This has increased the penetration level of wind power into existing distribution networks in many countries. (Author)

An introduction to reactive power compensation for wind farms

International Nuclear Information System (INIS)

Nigim, K.A.; Cairo Univ., Giza; Zobaa, A.F.; El Amin, I.

2005-01-01

The paper summarises the refereed contributions of seven articles reviewed for publication in the IJETP - Special Issue on 'Reactive compensation for wind farms'. The main goal of the special issue is to provide a forum to exchange information on the reactive power compensation requirements for wind farms and introducing possible price mechanisms for today's deregulated power industry. Uncompensated reactive power causes stress on the hosting utility grid as well as added expenses, which create in difficulties for power purchasing agreements from independent wind energy producers. Wind power producers need to comply with the hosting utility grid interconnection standards, e.g., voltage and frequency, as well as to provide controllable active and reactive sources of power. Active power supply is mainly dependent on the potential of wind power produced and the turbine design. Reactive power demand on the other hand depends on the conversion devices and the recovered power quantity fed to the grid. Static Var Compensators (SVC), Unified Power Quality Conditioners (UPQC), Unified Power Flow Controllers (UPFC), and the Distributed Static Synchronous Compensators (DSTATCOM) are all new emerging devices aimed at regulating the reactive power requirements. The excellent controllability of these devices has paved the way to flexible and dynamic controllers that are capable of regulating the flow of active and reactive power components. These devices are now suggested for the control of the reactive power requirement of wind generators. Studies have demonstrated acceptable voltage stabilisation results. This has increased the penetration level of wind power into existing distribution networks in many countries. (Author)

Mechanisms and neuronal networks involved in reactive and proactive cognitive control of interference in working memory.

Science.gov (United States)

Irlbacher, Kerstin; Kraft, Antje; Kehrer, Stefanie; Brandt, Stephan A

2014-10-01

Cognitive control can be reactive or proactive in nature. Reactive control mechanisms, which support the resolution of interference, start after its onset. Conversely, proactive control involves the anticipation and prevention of interference prior to its occurrence. The interrelation of both types of cognitive control is currently under debate: Are they mediated by different neuronal networks? Or are there neuronal structures that have the potential to act in a proactive as well as in a reactive manner? This review illustrates the way in which integrating knowledge gathered from behavioral studies, functional imaging, and human electroencephalography proves useful in answering these questions. We focus on studies that investigate interference resolution at the level of working memory representations. In summary, different mechanisms are instrumental in supporting reactive and proactive control. Distinct neuronal networks are involved, though some brain regions, especially pre-SMA, possess functions that are relevant to both control modes. Therefore, activation of these brain areas could be observed in reactive, as well as proactive control, but at different times during information processing. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemical reactivity of alkali lignin modified with laccase

International Nuclear Information System (INIS)

Sun, Yong; Qiu, Xueqing; Liu, Yunquan

2013-01-01

The modification of alkali lignin with laccase was investigated. The structural change of lignin was analyzed. The sulfonation reactivity was measured by the content of sulfonic group. The results showed the sulfonation reactivity increased to some extent under the condition of atmosphere pressure, but decreased under the condition of 0.3 MPa oxygen pressure. The analysis of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) showed the cleavage of various ether linkages and demethylation took place in the structure of lignin to certain extent during modification with laccase, which contributed to the improvement of sulfonation reactivity. Under the condition of 0.3 MPa oxygen pressure, the ratio of s/g (guaiacyl/syringyl) increased after modification, which reduced the sulfonation reactivity of lignin. Simultaneously partial polymerization reaction, such as 4-O-5′, β-5, 5-5 and other reaction in the aromatic ring decreased the activity sites of C 2 , C 5 and C 6 . Abundant polymerization reaction of α-O increased steric hindrance of C 2 and C 6 in aromatic ring, resulting in low sulfonation reactivity of lignin. -- Highlights: ► The modification of alkali lignin with laccase was investigated. ► The sulfonation reactivity increased under the condition of atmosphere pressure. ► More content of guaiacyl and hydroxy, the less content of methoxyl, syringyl can enhance the sulfonation reactivity of lignin. ► Partial moieties polymerized each other with α-O linkgages during treatment with laccase under oxygen pressure. ► The steric hindrance on C 2 and C 6 in aromatic ring resulted in low sulfonation reaction reactivity of lignin

Influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with carcinogenic and anticoagulant effect of 17β-aminoestrogens

Energy Technology Data Exchange (ETDEWEB)

Soriano-Correa, Catalina, E-mail: socc@puma2.zaragoza.unam.mx [Química Computacional, FES-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, Mexico City (Mexico); Raya, Angélica [Unidad Profesional Interdisciplinaria de Ingeniería Campus Guanajuato, Instituto Politécnico Nacional (IPN), Silao de la Victoria, Guanajuato (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz - Boca del Río, Universidad Veracruzana, Veracruz (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), Mexico City (Mexico)

2014-06-25

Highlights: • The aromatic A-ring of 17β-aminoestrogens contribute to its anticoagulant effect. • The electron-donor substituent groups favored the basicity of 17β-aminoestrogens. • The physicochemical properties are important in the carcinogenic effect of anticoagulant molecules. - Abstract: Activity of steroid hormones is dependent upon a number of factors, as solubility, transport and metabolism. The functional differences caused by structural modifications could exert an influence on the chemical reactivity and biological effect. The goal of this work is to study the influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with the carcinogenic risk that can associate with the anticoagulant effect of 17β-aminoestrogens using quantum-chemical descriptors at the DFT-B3LYP, BH and HLYP and M06-2X levels. The relative acidity of (H1) of the hydroxyl group increases with electron-withdrawing groups. Electron-donor groups favor the basicity. The steric hindrance of the substituents decreases the aromatic character and consequently diminution the carcinogenic effect. Density descriptors: hardness, electrophilic index, atomic charges, molecular orbitals, electrostatic potential and their geometric parameters permit analyses of the chemical reactivity and physicochemical features and to identify some reactive sites of 17β-aminoestrogens.

Letter: Modeling reactive shock waves in heterogeneous solids at the continuum level with stochastic differential equations

Science.gov (United States)

Kittell, D. E.; Yarrington, C. D.; Lechman, J. B.; Baer, M. R.

2018-05-01

A new paradigm is introduced for modeling reactive shock waves in heterogeneous solids at the continuum level. Inspired by the probability density function methods from turbulent reactive flows, it is hypothesized that the unreacted material microstructures lead to a distribution of heat release rates from chemical reaction. Fluctuations in heat release, rather than velocity, are coupled to the reactive Euler equations which are then solved via the Riemann problem. A numerically efficient, one-dimensional hydrocode is used to demonstrate this new approach, and simulation results of a representative impact calculation (inert flyer into explosive target) are discussed.

A comparative study of changes in immunological reactivity during prolonged introduction of radioactive and chemical substances into the organism with drinking water

International Nuclear Information System (INIS)

Shubik, V.M.; Nevstrueva, M.A.; Kalnitskij, S.A.; Livshits, R.E.; Merkushev, G.N.; Pilshchik, E.M.; Ponomareva, T.V.

1978-01-01

A comparative study was conducted into the factors of non-specific protection and specific immunity, allergic and autoallergic reactivities during prolonged exposure of experimental animals to 6 different radioactive and 7 harmful chemical substances. Qualitative and quantitative peculiarities were found in the changes in immunological reactivity during the exposure of the organism to radionuclides and stable chemical compounds. Impairment of immunity plays an essential role in the course and the outcome of effects induced by chronic action of the substances examined. (author)

Sputtered titanium oxynitride coatings for endosseous applications: Physical and chemical evaluation and first bioactivity assays

Energy Technology Data Exchange (ETDEWEB)

Banakh, Oksana, E-mail: oksana.banakh@he-arc.ch [Institute of Applied Microtechnologies, Haute Ecole Arc Ingénierie (HES-SO), Eplatures-Grise 17, CH-2300 La Chaux-de-Fonds (Switzerland); Moussa, Mira, E-mail: mira.moussa@unige.ch [Laboratory of Biomaterials, University of Geneva, 19, rue Barthelemy Menn, CH-1205 Geneva (Switzerland); Matthey, Joel, E-mail: joel.matthey@he-arc.ch [Institute of Applied Microtechnologies, Haute Ecole Arc Ingénierie (HES-SO), Eplatures-Grise 17, CH-2300 La Chaux-de-Fonds (Switzerland); Pontearso, Alessandro, E-mail: alessandro.pontearso@he-arc.ch [Institute of Applied Microtechnologies, Haute Ecole Arc Ingénierie (HES-SO), Eplatures-Grise 17, CH-2300 La Chaux-de-Fonds (Switzerland); Cattani-Lorente, Maria, E-mail: maria.cattani-lorente@unige.ch [Laboratory of Biomaterials, University of Geneva, 19, rue Barthelemy Menn, CH-1205 Geneva (Switzerland); Sanjines, Rosendo, E-mail: rosendo.sanjines@epfl.ch [Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Condensed Matter Physics, Station 3, CH-1015 Lausanne (Switzerland); Fontana, Pierre, E-mail: Pierre.Fontana@hcuge.ch [Haemostasis laboratory, Geneva University Hospital, Rue Gabrielle-Perret-Gentil 4, CH-1205 Geneva (Switzerland); Wiskott, Anselm, E-mail: anselm.wiskott@unige.ch [Laboratory of Biomaterials, University of Geneva, 19, rue Barthelemy Menn, CH-1205 Geneva (Switzerland); Durual, Stephane, E-mail: stephane.durual@unige.ch [Laboratory of Biomaterials, University of Geneva, 19, rue Barthelemy Menn, CH-1205 Geneva (Switzerland)

2014-10-30

Highlights: • Titanium oxynitride coatings (TiN{sub x}O{sub y}) with chemical composition ranging from TiN to TiO{sub 2} were deposited by magnetron sputtering from a metallic Ti target using a mixture of O{sub 2} + N{sub 2}. • The coatings structure as well as physical, chemical and mechanical properties progressively changes as a function of oxygen content in the TiN{sub x}O{sub y.} • All TiN{sub x}O{sub y} coatings show a significantly higher level of bioactivity as compared to bare Ti substrates (1.2 to 1.4 fold increase in cell proliferation). Despite variations in surface chemistry, topography and surface tension observed on films as a function of chemical composition, no significant differences in the films’ biological activity were observed after 3 days of testing. - Abstract: Titanium oxynitride coatings (TiN{sub x}O{sub y}) are considered a promising material for applications in dental implantology due to their high corrosion resistance, their biocompatibility and their superior hardness. Using the sputtering technique, TiN{sub x}O{sub y} films with variable chemical compositions can be deposited. These films may then be set to a desired value by varying the process parameters, that is, the oxygen and nitrogen gas flows. To improve the control of the sputtering process with two reactive gases and to achieve a variable and controllable coating composition, the plasma characteristics were monitored in-situ by optical emission spectroscopy. TiN{sub x}O{sub y} films were deposited onto commercially pure (ASTM 67) microroughened titanium plates by reactive magnetron sputtering. The nitrogen gas flow was kept constant while the oxygen gas flow was adjusted for each deposition run to obtain films with different oxygen and nitrogen contents. The physical and chemical properties of the deposited films were analyzed as a function of oxygen content in the titanium oxynitride. The potential application of the coatings in dental implantology was assessed by

Numerical investigation on the effect of reactivity gradient in an RCCI engine fueled with gasoline and diesel

International Nuclear Information System (INIS)

Li, J.; Yang, W.M.; An, H.; Zhou, D.Z.; Yu, W.B.; Wang, J.X.; Li, L.

2015-01-01

Highlights: • A chemical reaction mechanism is newly developed for dual fuel combustion. • The developed chemical kinetics is coupled with KIVA4 to model the combustion. • The role of reactivity gradient in RCCI combustion is investigated. • The RCCI (dual fuel mode) combustion is compared with blend fuel mode. - Abstract: The reactivity controlled compression ignition (RCCI), which belongs to dual fuel mode (DFM) combustion has been considered as a promising way to achieve high fuel conversion efficiency and low emissions. By this strategy, a fuel reactivity gradient is formed in the combustion chamber which offers the probability of controlling combustion phasing. In this study, the role of fuel reactivity gradient was examined numerically by comparing a DFM (i.e., RCCI) combustion with other hypothetical cases under one specific load condition. Firstly, a chemical reaction mechanism was developed aiming at a modelling study on dual fuel and blend fuel combustion in internal combustion (IC) engines fueled by gasoline/diesel and gasoline/biodiesel. Ignition delays were validated for 100% diesel, 100% gasoline and 100% biodiesel under 102 conditions in total. Subsequently, the validated reaction mechanism which consists of 107 species and 425 reactions was implemented in coupled KIVA4-CHEMKIN code. Three dimensional validations were further conducted under 3 conditions including pure diesel combustion, and gasoline/diesel DFM combustion with both single and double injection strategies in the engine. To investigate the fuel reactivity gradient, the gasoline/diesel DFM combustion with single injection was compared with other three hypothetical cases, one of which was DFM without fuel reactivity gradient, two were the blend fuel mode but with different start of injection (SOI) timings. The results showed that the fuel reactivity gradient could retard the ignition timing, reduce heat release rate, and ease peak pressure rise rate. In addition, low levels of NO

Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies.

Science.gov (United States)

Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

2017-08-01

Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH 2 -CH=CH-CH 2 -) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than ~1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies

Science.gov (United States)

Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

2017-08-01

Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH2-CH=CH-CH2-) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than 1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

MoMaS reactive transport benchmark using PFLOTRAN

Science.gov (United States)

Park, H.

2017-12-01

MoMaS benchmark was developed to enhance numerical simulation capability for reactive transport modeling in porous media. The benchmark was published in late September of 2009; it is not taken from a real chemical system, but realistic and numerically challenging tests. PFLOTRAN is a state-of-art massively parallel subsurface flow and reactive transport code that is being used in multiple nuclear waste repository projects at Sandia National Laboratories including Waste Isolation Pilot Plant and Used Fuel Disposition. MoMaS benchmark has three independent tests with easy, medium, and hard chemical complexity. This paper demonstrates how PFLOTRAN is applied to this benchmark exercise and shows results of the easy benchmark test case which includes mixing of aqueous components and surface complexation. Surface complexations consist of monodentate and bidentate reactions which introduces difficulty in defining selectivity coefficient if the reaction applies to a bulk reference volume. The selectivity coefficient becomes porosity dependent for bidentate reaction in heterogeneous porous media. The benchmark is solved by PFLOTRAN with minimal modification to address the issue and unit conversions were made properly to suit PFLOTRAN.

Reactivity study on thermal cracking of vacuum residues

Science.gov (United States)

León, A. Y.; Díaz, S. D.; Rodríguez, R. C.; Laverde, D.

2016-02-01

This study focused on the process reactivity of thermal cracking of vacuum residues from crude oils mixtures. The thermal cracking experiments were carried out under a nitrogen atmosphere at 120psi between 430 to 500°C for 20 minutes. Temperature conditions were established considering the maximum fractional conversion reported in tests of thermogravimetry performed in the temperature range of 25 to 600°C, with a constant heating rate of 5°C/min and a nitrogen flow rate of 50ml/min. The obtained products were separated in to gases, distillates and coke. The results indicate that the behaviour of thermal reactivity over the chemical composition is most prominent for the vacuum residues with higher content of asphaltenes, aromatics, and resins. Finally some correlations were obtained in order to predict the weight percentage of products from its physical and chemical properties such as CCR, SARA (saturates, aromatics, resins, asphaltenes) and density. The results provide new knowledge of the effect of temperature and the properties of vacuum residues in thermal conversion processes.

The relationship between fractional flow reserve, platelet reactivity and platelet leukocyte complexes in stable coronary artery disease

NARCIS (Netherlands)

Sels, J.W.E.M.; Rutten, B.; Holten, van T.C.; Hillaert, M.A.K.; Waltenberger, J.; Pijls, N.H.J.; Pasterkamp, G.; Groot, de P.G.; Roest, M.

2013-01-01

Background: The presence of stenoses that significantly impair blood flow and cause myocardial ischemia negatively affects prognosis of patients with stable coronary artery disease. Altered platelet reactivity has been associated with impaired prognosis of stable coronary artery disease. Platelets

Coupled energy and reactive power market clearing considering power system security

International Nuclear Information System (INIS)

Rabiee, Abdorreza; Shayanfar, Heidarali; Amjady, Nima

2009-01-01

In a deregulated environment, when talking about electricity markets, one usually refers to energy market, paying less attention to the reactive power market. Active and reactive powers are, however, coupled through the AC power flow equations and branch loading limits as well as the synchronous generators capability curves. However, the sequential approach for energy and reactive power markets cannot present the optimal solution due to the interactions between these markets. For instance, clearing of the reactive power market can change active power dispatch (e.g. due to a change of transmission system losses and the capability curve limitation), which can lead to degradation of the energy market clearing point. This paper presents a coupled day ahead energy and reactive power market based on the pay-at-MCP settlement mechanism. Besides, the proposed coupled framework considers voltage stability and security issues and branch loading limits. The coupled market is cleared through optimal power flow (OPF). Its objective function includes total payment of generating units for their active power production along with the total payment function (TPF) of units for their reactive power compensation. Moreover, lost opportunity cost (LOC) of the units is also considered. The effectiveness of the proposed framework is examined on the IEEE 24 bus Reliability Test System

Coupled energy and reactive power market clearing considering power system security

Energy Technology Data Exchange (ETDEWEB)

Rabiee, Abdorreza; Shayanfar, Heidarali [Center of Excellence for Power System Automation and Operation, Electrical Engineering Department, Iran University of Science and Technology (IUST), Tehran (Iran); Amjady, Nima [Department of Electrical Engineering, Semnan University, Semnan (Iran)

2009-04-15

In a deregulated environment, when talking about electricity markets, one usually refers to energy market, paying less attention to the reactive power market. Active and reactive powers are, however, coupled through the AC power flow equations and branch loading limits as well as the synchronous generators capability curves. However, the sequential approach for energy and reactive power markets cannot present the optimal solution due to the interactions between these markets. For instance, clearing of the reactive power market can change active power dispatch (e.g. due to a change of transmission system losses and the capability curve limitation), which can lead to degradation of the energy market clearing point. This paper presents a coupled day ahead energy and reactive power market based on the pay-at-MCP settlement mechanism. Besides, the proposed coupled framework considers voltage stability and security issues and branch loading limits. The coupled market is cleared through optimal power flow (OPF). Its objective function includes total payment of generating units for their active power production along with the total payment function (TPF) of units for their reactive power compensation. Moreover, lost opportunity cost (LOC) of the units is also considered. The effectiveness of the proposed framework is examined on the IEEE 24 bus Reliability Test System. (author)

Reactive Minerals and Dechlorinating Communities: Mechanisms Governing the Degradation of Chlorinated Ethenes during Back Diffusion from Low Permeability Zones in Aerobic and Anaerobic Environments

Science.gov (United States)

Berns, E. C.; Zeng, R.; Singh, H.; Valocchi, A. J.; Sanford, R. A.; Strathmann, T. J.; Schaefer, C. E.; Werth, C. J.

2017-12-01

Low permeability zones (LPZs) comprised of silts and clays, and contaminated with chlorinated ethenes, can act as a long term source of contaminated groundwater by diffusion into adjacent high permeability zones (HPZs). Following initial remediation efforts, chlorinated ethenes that have diffused into LPZs will back diffuse and recontaminate HPZs. Because chlorinated ethenes are known to cause cancer and damage the liver, kidneys, and central nervous system, it is important to understand how they degrade in natural systems and how to model their fate and transport. Previous work has shown that anaerobic hydrogenolysis reactions are facilitated by both dechlorinating microorganisms and reactive minerals. Abiotic dichloro-elimination reactions with reactive minerals can also degrade chlorinated ethenes to acetylene, albeit at slower rates than biotic processes. More recently, studies have explored aerobic abiotic degradation of chlorinated ethenes to formate, glycolate, and carbon dioxide. This study focuses on these biotic and abiotic reactions and their contributions to chlorinated ethene degradation under aerobic and anaerobic conditions at the LPZ/HPZ interface. A two-dimensional flow cell was constructed to model this interface using clay and sand from Pease Air Force Base. The clay was inoculated with a dechlorinating enrichment culture. Tenax adsorbent beads equilibrated with trichloroethylene (TCE) were used as a chlorinated ethene source zone at the base of the clay. TCE and its degradation products diffused from the clay into the sand, where they were removed from the flow cell by groundwater at a rate of 50 mL/day. Volatile compounds were trapped in a sample loop and removed every 48 hours for analysis by GC-FID. Organic and inorganic ions in the effluent were analyzed on the HPLC and IC. The experiment was terminated by freezing the flow cell, and chemical profiles through the flow cell material were created to show the spatial distribution of degradation

The Importance of Protons in Reactive Transport Modeling

Science.gov (United States)

McNeece, C. J.; Hesse, M. A.

2014-12-01

The importance of pH in aqueous chemistry is evident; yet, its role in reactive transport is complex. Consider a column flow experiment through silica glass beads. Take the column to be saturated and flowing with solution of a distinct pH. An instantaneous change in the influent solution pH can yield a breakthrough curve with both a rarefaction and shock component (composite wave). This behavior is unique among aqueous ions in transport and is more complex than intuition would tell. Analysis of the hyperbolic limit of this physical system can explain these first order transport phenomenon. This analysis shows that transport behavior is heavily dependent on the shape of the adsorption isotherm. Hence it is clear that accurate surface chemistry models are important in reactive transport. The proton adsorption isotherm has nonconstant concavity due to the proton's ability to partition into hydroxide. An eigenvalue analysis shows that an inflection point in the adsorption isotherm allows the development of composite waves. We use electrostatic surface complexation models to calculate realistic proton adsorption isotherms. Surface characteristics such as specific surface area, and surface site density were determined experimentally. We validate the model by comparison against silica glass bead flow through experiments. When coupled to surface complexation models, the transport equation captures the timing and behavior of breakthrough curves markedly better than with commonly used Langmuir assumptions. Furthermore, we use the adsorption isotherm to predict, a priori, the transport behavior of protons across pH composition space. Expansion of the model to multicomponent systems shows that proton adsorption can force composite waves to develop in the breakthrough curves of ions that would not otherwise exhibit such behavior. Given the abundance of reactive surfaces in nature and the nonlinearity of chemical systems, we conclude that building a greater understanding of

Properties of amorphous silicon thin films synthesized by reactive particle beam assisted chemical vapor deposition

International Nuclear Information System (INIS)

Choi, Sun Gyu; Wang, Seok-Joo; Park, Hyeong-Ho; Jang, Jin-Nyoung; Hong, MunPyo; Kwon, Kwang-Ho; Park, Hyung-Ho

2010-01-01

Amorphous silicon thin films were formed by chemical vapor deposition of reactive particle beam assisted inductively coupled plasma type with various reflector bias voltages. During the deposition, the substrate was heated at 150 o C. The effects of reflector bias voltage on the physical and chemical properties of the films were systematically studied. X-ray diffraction and Raman spectroscopy results showed that the deposited films were amorphous and the films under higher reflector voltage had higher internal energy to be easily crystallized. The chemical state of amorphous silicon films was revealed as metallic bonding of Si atoms by using X-ray photoelectron spectroscopy. An increase in reflector voltage induced an increase of surface morphology of films and optical bandgap and a decrease of photoconductivity.

Investigation on reactivity of iron nickel oxides in chemical looping dry reforming

International Nuclear Information System (INIS)

Huang, Zhen; He, Fang; Chen, Dezhen; Zhao, Kun; Wei, Guoqiang; Zheng, Anqing; Zhao, Zengli; Li, Haibin

2016-01-01

Iron nickel oxides as oxygen carriers were investigated to clarify the reaction mechanism of NiFe_2O_4 material during the chemical looping dry reforming (CLDR) process. The thermodynamic analysis showed that metallic Fe can be oxidized into Fe_3O_4 by CO_2, but metallic Ni cannot. The oxidizability of the four oxygen carriers was in the order of NiO > synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3, and the reducibility sequence of their reduced products was synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3 > NiO. The NiO showed the best oxidizability but it was easy to cause CH_4 cracking and its reduced product (Ni) did not recover lattice oxygen under CO_2 atmosphere. It only produced 74 mL CO for 1 g Fe_2O_3 during the CO_2 reforming because of its weak oxidizability. The Redox ability of synthetic NiFe_2O_4 was obvious higher than that of NiO-Fe_2O_3 mixed oxides due to the synergistic effect of metallic Fe-Ni in the spinel structure. 1 g synthetic NiFe_2O_4 can produce 238 mL CO, which was twice higher than that of 1 g NiO-Fe_2O_3 mixed oxides (111 mL). A part of Fe element was divorced from the NiFe_2O_4 spinel structure after one cycle, which was the major reason for degradation of reactivity of NiFe_2O_4 oxygen carrier. - Highlights: • A synergistic effect of Fe/Ni can improve the reactivity of oxygen carrier (OC). • The oxidizability sequence of four OCs is NiO > NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3. • The reducibility sequence of four OCs is NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3 > NiO. • The formation of Fe (Ni) alloy phase facilitates more CO_2 reduced into CO. • Part of Fe is divorced from the spinel structure, leading to the degeneration of OC reactivity.

Influence of crystal defects on the chemical reactivity of recoil atoms in oxygen-containing chromium compounds

International Nuclear Information System (INIS)

Costea, T.

1969-01-01

The influence of crystal defects on the chemical reactivity of recoil atoms produced by the reaction 50 Cr (n,γ) 51 Cr in oxygen-containing chromium compounds has been studied. Three methods have been used to introduce the defects: doping (K 2 CrO 4 doped with BaCrO 4 ), irradiation by ionizing radiation (K 2 CrO 4 irradiated in the presence of Li 2 CO 3 ) and non-stoichiometry (the semi-conducting oxides of the CrO 3 -Cr 2 O 3 series). The thermal annealing kinetics of the irradiated samples have been determined, and the activation energy has been calculated. In all cases it has been observed that there is a decrease in the activation energy for thermal annealing in the presence of the defects. In order to explain the annealing process, an electronic mechanism has been proposed based on the interaction between the recoil species and the charge-carriers (holes or electrons). (author) [fr

A numerical analysis for non-linear radiation in MHD flow around a cylindrical surface with chemically reactive species

Directory of Open Access Journals (Sweden)

Junaid Ahmad Khan

2018-03-01

Full Text Available Boundary layer flow around a stretchable rough cylinder is modeled by taking into account boundary slip and transverse magnetic field effects. The main concern is to resolve heat/mass transfer problem considering non-linear radiative heat transfer and temperature/concentration jump aspects. Using conventional similarity approach, the equations of motion and heat transfer are converted into a boundary value problem whose solution is computed by shooting method for broad range of slip coefficients. The proposed numerical scheme appears to improve as the strengths of magnetic field and slip coefficients are enhanced. Axial velocity and temperature are considerably influenced by a parameter M which is inversely proportional to the radius of cylinder. A significant change in temperature profile is depicted for growing wall to ambient temperature ratio. Relevant physical quantities such as wall shear stress, local Nusselt number and local Sherwood number are elucidated in detail. Keywords: Stretchable boundary, Thermal radiation, Chemical reaction, Mathematical modeling, Non-linear differential system, Mass transfer

Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

International Nuclear Information System (INIS)

Hamaguchi, Satoshi

2013-01-01

Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed

Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

Energy Technology Data Exchange (ETDEWEB)

Hamaguchi, Satoshi [Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

2013-07-11

Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

INFLUENCE OF GROUNDWATER GEOCHEMISTRY ON THE LONG-TERM PERFORMANCE OF IN-SITU PERMEABLE REACTIVE BARRIERS CONTAINING ZERO-VALENT IRON

Science.gov (United States)

Reactive barriers that couple subsurface fluid flow with a passive chemical treatment zone are emerging, cost effective approaches for in-situ remediation of contaminated groundwater. Factors such as the build-up of surface precipitates, bio-fouling, and changes in subsurface tr...

Stable isotope reactive transport modeling in water-rock interactions during CO2 injection

Science.gov (United States)

Hidalgo, Juan J.; Lagneau, Vincent; Agrinier, Pierre

2010-05-01

Stable isotopes can be of great usefulness in the characterization and monitoring of CO2 sequestration sites. Stable isotopes can be used to track the migration of the CO2 plume and identify leakage sources. Moreover, they provide unique information about the chemical reactions that take place on the CO2-water-rock system. However, there is a lack of appropriate tools that help modelers to incorporate stable isotope information into the flow and transport models used in CO2 sequestration problems. In this work, we present a numerical tool for modeling the transport of stable isotopes in groundwater reactive systems. The code is an extension of the groundwater single-phase flow and reactive transport code HYTEC [2]. HYTEC's transport module was modified to include element isotopes as separate species. This way, it is able to track isotope composition of the system by computing the mixing between the background water and the injected solution accounting for the dependency of diffusion on the isotope mass. The chemical module and database have been expanded to included isotopic exchange with minerals and the isotope fractionation associated with chemical reactions and mineral dissolution or precipitation. The performance of the code is illustrated through a series of column synthetic models. The code is also used to model the aqueous phase CO2 injection test carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) [1]. References [1] N. Assayag, J. Matter, M. Ader, D. Goldberg, and P. Agrinier. Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects. Chemical Geology, 265(1-2):227-235, July 2009. [2] Jan van der Lee, Laurent De Windt, Vincent Lagneau, and Patrick Goblet. Module-oriented modeling of reactive transport with HYTEC. Computers & Geosciences, 29(3):265-275, April 2003.

Swirling flow in bileaflet mechanical heart valve

Science.gov (United States)

Gataulin, Yakov A.; Khorobrov, Svyatoslav V.; Yukhnev, Andrey D.

2018-05-01

Bileaflet mechanical valves are most commonly used for heart valve replacement. Nowadays swirling blood flow is registered in different parts of the cardiovascular system: left ventricle, aorta, arteries and veins. In present contribution for the first time the physiological swirling flow inlet conditions are used for numerical simulation of aortic bileaflet mechanical heart valve hemodynamics. Steady 3-dimensional continuity and RANS equations are employed to describe blood motion. The Menter SST model is used to simulate turbulence effects. Boundary conditions are corresponded to systolic peak flow. The domain was discretized into hybrid tetrahedral and hexahedral mesh with an emphasis on wall boundary layer. A system of equations was solved in Ansys Fluent finite-volume package. Noticeable changes in the flow structure caused by inlet swirl are shown. The swirling flow interaction with the valve leaflets is analyzed. A central orifice jet changes its cross-section shape, which leads to redistribution of wall shear stress on the leaflets. Transvalvular pressure gradient and area-averaged leaflet wall shear stress increase. Physiological swirl intensity noticeably reduces downstream of the valve.

On the fluid mechanics of fires

Energy Technology Data Exchange (ETDEWEB)

TIESZEN,SHELDON R.

2000-02-29

Fluid mechanics research related to fire is reviewed with focus on canonical flows, multiphysics coupling aspects, experimental and numerical techniques. Fire is a low-speed, chemically-reacting, flow in which buoyancy plans an important role. Fire research has focused on two canonical flows, the reacting boundary-layer and the reacting free plume. There is rich, multi-lateral, bi-directional, coupling among fluid mechanics and scalar transport, combustion, and radiation. There is only a limited experimental fluid-mechanics database for fire due to measurement difficulties in the harsh environment, and the focus within the fire community on thermal/chemical consequences. Increasingly, computational fluid dynamics techniques are being used to provide engineering guidance on thermal/chemical consequences and to study fire phenomenology.

Non-domestic phosphorus release in rivers during low-flow: Mechanisms and implications for sources identification

Science.gov (United States)

Dupas, Rémi; Tittel, Jörg; Jordan, Phil; Musolff, Andreas; Rode, Michael

2018-05-01

A common assumption in phosphorus (P) load apportionment studies is that P loads in rivers consist of flow independent point source emissions (mainly from domestic and industrial origins) and flow dependent diffuse source emissions (mainly from agricultural origin). Hence, rivers dominated by point sources will exhibit highest P concentration during low-flow, when flow dilution capacity is minimal, whereas rivers dominated by diffuse sources will exhibit highest P concentration during high-flow, when land-to-river hydrological connectivity is maximal. Here, we show that Soluble Reactive P (SRP) concentrations in three forested catchments free of point sources exhibited seasonal maxima during the summer low-flow period, i.e. a pattern expected in point source dominated areas. A load apportionment model (LAM) is used to show how point sources contribution may have been overestimated in previous studies, because of a biogeochemical process mimicking a point source signal. Almost twenty-two years (March 1995-September 2016) of monthly monitoring data of SRP, dissolved iron (Fe) and nitrate-N (NO3) were used to investigate the underlying mechanisms: SRP and Fe exhibited similar seasonal patterns and opposite to that of NO3. We hypothesise that Fe oxyhydroxide reductive dissolution might be the cause of SRP release during the summer period, and that NO3 might act as a redox buffer, controlling the seasonality of SRP release. We conclude that LAMs may overestimate the contribution of P point sources, especially during the summer low-flow period, when eutrophication risk is maximal.

Constraining a compositional flow model with flow-chemical data using an ensemble-based Kalman filter

KAUST Repository

Gharamti, M. E.; Kadoura, A.; Valstar, J.; Sun, S.; Hoteit, Ibrahim

2014-01-01

Isothermal compositional flow models require coupling transient compressible flows and advective transport systems of various chemical species in subsurface porous media. Building such numerical models is quite challenging and may be subject to many sources of uncertainties because of possible incomplete representation of some geological parameters that characterize the system's processes. Advanced data assimilation methods, such as the ensemble Kalman filter (EnKF), can be used to calibrate these models by incorporating available data. In this work, we consider the problem of estimating reservoir permeability using information about phase pressure as well as the chemical properties of fluid components. We carry out state-parameter estimation experiments using joint and dual updating schemes in the context of the EnKF with a two-dimensional single-phase compositional flow model (CFM). Quantitative and statistical analyses are performed to evaluate and compare the performance of the assimilation schemes. Our results indicate that including chemical composition data significantly enhances the accuracy of the permeability estimates. In addition, composition data provide more information to estimate system states and parameters than do standard pressure data. The dual state-parameter estimation scheme provides about 10% more accurate permeability estimates on average than the joint scheme when implemented with the same ensemble members, at the cost of twice more forward model integrations. At similar computational cost, the dual approach becomes only beneficial after using large enough ensembles.

Constraining a compositional flow model with flow-chemical data using an ensemble-based Kalman filter

KAUST Repository

Gharamti, M. E.

2014-03-01

Isothermal compositional flow models require coupling transient compressible flows and advective transport systems of various chemical species in subsurface porous media. Building such numerical models is quite challenging and may be subject to many sources of uncertainties because of possible incomplete representation of some geological parameters that characterize the system\\'s processes. Advanced data assimilation methods, such as the ensemble Kalman filter (EnKF), can be used to calibrate these models by incorporating available data. In this work, we consider the problem of estimating reservoir permeability using information about phase pressure as well as the chemical properties of fluid components. We carry out state-parameter estimation experiments using joint and dual updating schemes in the context of the EnKF with a two-dimensional single-phase compositional flow model (CFM). Quantitative and statistical analyses are performed to evaluate and compare the performance of the assimilation schemes. Our results indicate that including chemical composition data significantly enhances the accuracy of the permeability estimates. In addition, composition data provide more information to estimate system states and parameters than do standard pressure data. The dual state-parameter estimation scheme provides about 10% more accurate permeability estimates on average than the joint scheme when implemented with the same ensemble members, at the cost of twice more forward model integrations. At similar computational cost, the dual approach becomes only beneficial after using large enough ensembles.

Reactive Flow Control of Delta Wing Vortex (Postprint)

Science.gov (United States)

2006-08-01

wing aircraft. A substantial amount of research has been dedicated to the control of aerodynamic flows using both passive and active control mechanisms...Passive vortex control devices such as vortex generators and winglets attach to the wing and require no energy input. Passive vortex control...leading edges is also effective for changing the aerodynamic characteristics of delta wings [2] [3]. Gutmark and Guillot [5] proposed controlling

Numerical investigation on MHD micropolar fluid flow toward a stagnation point on a vertical surface with heat source and chemical reaction

Directory of Open Access Journals (Sweden)

S. Baag

2017-01-01

Full Text Available In this paper, the steady magnetohydrodynamic (MHD mixed convection stagnation point flow of an incompressible and electrically conducting micropolar fluid past a vertical flat plate is investigated. The effects of induced magnetic field, heat generation/absorption and chemical reaction have been taken into account during the present study. Numerical solutions are obtained by using the Runge–Kutta fourth order scheme with shooting technique. The skin friction and rate of heat and mass transfer at the bounding surface are also calculated. The generality of the present study is assured of by discussing the works of Ramachandran et al. (1988, Lok et al. (2005 and Ishak et al. (2008 as particular cases. It is interesting to note that the results of the previous authors are in good agreement with the results of the present study tabulated which is evident from the tabular values. Further, the novelty of the present analysis is to account for the effects of first order chemical reaction in a flow of reactive diffusing species in the presence of heat source/sink. The discussion of the present study takes care of both assisting and opposing flows. From the computational aspect, it is remarked that results of finite difference (Ishak et al. (2008 and Runge–Kutta associated with shooting technique (present method yield same numerical results with a certain degree of accuracy. It is important to note that the thermal buoyancy parameter in opposing flow acts as a controlling parameter to prevent back flow. Diffusion of lighter foreign species, suitable for initiating a destructive reaction, is a suggestive measure for reducing skin friction.

Novel Semi-Direct OH Reactivity (kOH) Measurements by Chemical Ionization Mass Spectrometry during a Chamber Instrument Comparison Campaign and Continuous Ambient Air Sampling at a Central European GAW Station

Science.gov (United States)

Muller, J.; Kubistin, D.; Elste, T.; Plass-Duelmer, C.; Claude, A.; Englert, J.; Holla, R.; Fuchs, H.; Hofzumahaus, A.; Holland, F.; Novelli, A.; Tillmann, R.; Wegener, R.; Rohrer, F.; Yu, Z.; Bohn, B.; Williams, J.; Pfannerstill, E.; Edtbauer, A.; Kluepfel, T.

2016-12-01

Total OH reactivity (kOH) has been recognized as a useful measure to gauge the potential atmospheric oxidation capacity and a few different in-situ measurement techniques have been developed over the last 15 years. Here results are presented from a novel semi-direct method developed by the German Weather Service (DWD) utilizing a chemical ionization mass spectrometer (CIMS). Recently in April 2016, the CIMS system participated in a half-blind kOH instrument comparison campaign at the Forschungszentrum Jülich (FZJ) SAPHIR chamber. Experiments provided controlled conditions with a range of different VOC mixtures and varying NOx levels, representing environments dominated by biogenic or urban emissions. Alongside CIMS, kOH was also measured by systems using the comparative reactivity method (CRM) and the pump-probe technique with OH detection. The intercomparison revealed a good performance of CIMS at lower OH reactivities (0-15 s-1), a range for which the instrumental set up was optimized. Limitations of the CIMS system consist of an upper limit for kOH detection and the need for applying a chemical correction function as a result of instrument-internal HOx recycling. Findings and instrument parameters obtained from the FZJ SAPHIR campaign and flow tube experiments are then applied to ambient air kOH measurements at the Meteorological Observatory Hohenpeissenberg (MOHp), Germany. The CIMS instrument is used there for long-term measurements of OH, H2SO4, ROx and kOH. Here, we show ambient air kOH measurements, interpreted in conjunction with volatile organic compounds (VOC) and inorganic trace gases also measured at the GAW station Hohenpeissenberg. These observations provide a unique dataset to investigate turnover rates and seasonal cycles of reactive trace gases, i.e. sources that make up total OH reactivity in this central European, rural setting.

Reactive oxygen species production and discontinuous gas exchange in insects

OpenAIRE

Boardman, Leigh; Terblanche, John S.; Hetz, Stefan K.; Marais, Elrike; Chown, Steven L.

2011-01-01

While biochemical mechanisms are typically used by animals to reduce oxidative damage, insects are suspected to employ a higher organizational level, discontinuous gas exchange mechanism to do so. Using a combination of real-time, flow-through respirometry and live-cell fluorescence microscopy, we show that spiracular control associated with the discontinuous gas exchange cycle (DGC) in Samia cynthia pupae is related to reactive oxygen species (ROS). Hyperoxia fails to increase mean ROS produ...

Analysis Of Convective Plane Stagnation Point Chemically Reactive Mhd Flow Past A Vertical Porous Plate With A Convective Boundary Condition In The Presence Of A Uniform Magnetic Field.

OpenAIRE

Adeniyan, A.,

2013-01-01

The numerical investigation of a stagnation point boundary layer flow , mass and heat transfer of a steady two dimensional , incompressible , viscous electrically conducting, chemically reacting laminar fluid over a vertical convectively heated , electrically neutral flat plate exposed to a transverse uniform magnetic field has been carried out to examine the influence of the simultaneous presence of the effects of a convective boundary condition, chemical reaction, heat transfer and suctio...

Influence of turbulent fluctuations on non-equilibrium chemical reactions in the flow

Science.gov (United States)

Molchanov, A. M.; Yanyshev, D. S.; Bykov, L. V.

2017-11-01

In chemically nonequilibrium flows the problem of calculation of sources (formation rates) in equations for chemical species is of utter importance. Formation rate of each component is a non-linear function of mixture density, temperature and concentration of species. Thus the suggestion that the mean rate may be determined via mean values of the flow parameters could lead to significant errors. One of the most accurate approaches here is utilization of probability density function (PDF). In this paper the method for constructing such PDFs is developed. The developed model was verified by comparison with the experimental data. On the example of supersonic combustion it was shown that while the overall effect on the averaged flow field is often negligible, the point of ignition can be considerably shifted up the flow.

Study on chemical mechanical polishing of silicon wafer with megasonic vibration assisted.

Science.gov (United States)

Zhai, Ke; He, Qing; Li, Liang; Ren, Yi

2017-09-01

Chemical mechanical polishing (CMP) is the primary method to realize the global planarization of silicon wafer. In order to improve this process, a novel method which combined megasonic vibration to assist chemical mechanical polishing (MA-CMP) is developed in this paper. A matching layer structure of polishing head was calculated and designed. Silicon wafers are polished by megasonic assisted chemical mechanical polishing and traditional chemical mechanical polishing respectively, both coarse polishing and precision polishing experiments were carried out. With the use of megasonic vibration, the surface roughness values Ra reduced from 22.260nm to 17.835nm in coarse polishing, and the material removal rate increased by approximately 15-25% for megasonic assisted chemical mechanical polishing relative to traditional chemical mechanical polishing. Average Surface roughness values Ra reduced from 0.509nm to 0.387nm in precision polishing. The results show that megasonic assisted chemical mechanical polishing is a feasible method to improve polishing efficiency and surface quality. The material removal and finishing mechanisms of megasonic vibration assisted polishing are investigated too. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanisms of nanotoxicity: generation of reactive oxygen species.

Science.gov (United States)

Fu, Peter P; Xia, Qingsu; Hwang, Huey-Min; Ray, Paresh C; Yu, Hongtao

2014-03-01

Nanotechnology is a rapidly developing field in the 21(st) century, and the commercial use of nanomaterials for novel applications is increasing exponentially. To date, the scientific basis for the cytotoxicity and genotoxicity of most manufactured nanomaterials are not understood. The mechanisms underlying the toxicity of nanomaterials have recently been studied intensively. An important mechanism of nanotoxicity is the generation of reactive oxygen species (ROS). Overproduction of ROS can induce oxidative stress, resulting in cells failing to maintain normal physiological redox-regulated functions. This in turn leads to DNA damage, unregulated cell signaling, change in cell motility, cytotoxicity, apoptosis, and cancer initiation. There are critical determinants that can affect the generation of ROS. These critical determinants, discussed briefly here, include: size, shape, particle surface, surface positive charges, surface-containing groups, particle dissolution, metal ion release from nanometals and nanometal oxides, UV light activation, aggregation, mode of interaction with cells, inflammation, and pH of the medium. Copyright © 2014. Published by Elsevier B.V.

Mechanisms of nanotoxicity: Generation of reactive oxygen species

Directory of Open Access Journals (Sweden)

Peter P. Fu

2014-03-01

Full Text Available Nanotechnology is a rapidly developing field in the 21st century, and the commercial use of nanomaterials for novel applications is increasing exponentially. To date, the scientific basis for the cytotoxicity and genotoxicity of most manufactured nanomaterials are not understood. The mechanisms underlying the toxicity of nanomaterials have recently been studied intensively. An important mechanism of nanotoxicity is the generation of reactive oxygen species (ROS. Overproduction of ROS can induce oxidative stress, resulting in cells failing to maintain normal physiological redox-regulated functions. This in turn leads to DNA damage, unregulated cell signaling, change in cell motility, cytotoxicity, apoptosis, and cancer initiation. There are critical determinants that can affect the generation of ROS. These critical determinants, discussed briefly here, include: size, shape, particle surface, surface positive charges, surface-containing groups, particle dissolution, metal ion release from nanometals and nanometal oxides, UV light activation, aggregation, mode of interaction with cells, inflammation, and pH of the medium.

Redox mechanism of reactive oxygen species in exercise

Directory of Open Access Journals (Sweden)

Feng He

2016-11-01

Full Text Available It is well known that regular exercise benefits health. However, unaccustomed and/or exhaustive exercise can generate excessive reactive oxygen species (ROS, leading to oxidative stress-related tissue damage and impaired muscle contractility. ROS are produced in both aerobic and anaerobic exercise. Although mitochondria, NADPH oxidases and xanthine oxidase have all been identified as contributors to ROS production, the exact redox mechanisms underlying exercise-induced oxidative stress remain elusive. Interestingly, moderate exposure to ROS is necessary to induce the body’s adaptive responses such as the activation of antioxidant defense mechanisms. Dietary antioxidant manipulation can also reduce ROS levels and muscle fatigue, as well as enhance exercise recovery. To elucidate the complex role of ROS in exercise, this article updates on new findings of ROS origins within skeletal muscles associated with various types of exercises such as endurance, sprint and mountain climbing, corresponding antioxidant defense systems as well as dietary manipulation against damage caused by ROS.

Evaluation of five strategies to limit the impact of fouling in permeable reactive barriers

International Nuclear Information System (INIS)

Li Lin; Benson, Craig H.

2010-01-01

Ground water flow and geochemical reactive transport models were used to assess the effectiveness of five strategies used to limit fouling and to enhance the long-term hydraulic behavior of continuous-wall permeable reactive barriers (PRBs) employing granular zero valent iron (ZVI). The flow model accounted for geological heterogeneity and the reactive transport model included a geochemical algorithm for simulating iron corrosion and mineral precipitation reactions that have been observed in ZVI PRBs. The five strategies that were evaluated are pea gravel equalization zones, a sacrificial pre-treatment zone, pH adjustment, large ZVI particles, and mechanical treatment. Results of simulations show that installation of pea gravel equalization zones results in flow equalization and a more uniform distribution of residence times within the PRB. Residence times within the PRB are less affected by mineral precipitation when a pre-treatment zone is employed. pH adjustment limits the total amount of hydroxide ions in ground water to reduce porosity reduction and to retain larger residence times. Larger ZVI particles reduce porosity reduction as a result of the smaller iron surface area for iron corrosion, and retain longer residence time. Mechanical treatment redistributes the porosity uniformly throughout the PRB over time, which is effective in maintaining residence time.

Computer tool to evaluate the cue reactivity of chemically dependent individuals.

Science.gov (United States)

Silva, Meire Luci da; Frère, Annie France; Oliveira, Henrique Jesus Quintino de; Martucci Neto, Helio; Scardovelli, Terigi Augusto

2017-03-01

Anxiety is one of the major influences on the dropout of relapse and treatment of substance abuse treatment. Chemically dependent individuals need (CDI) to be aware of their emotional state in situations of risk during their treatment. Many patients do not agree with the diagnosis of the therapist when considering them vulnerable to environmental stimuli related to drugs. This research presents a cue reactivity detection tool based on a device acquiring physiological signals connected to personal computer. Depending on the variations of the emotional state of the drug addict, alteration of the physiological signals will be detected by the computer tool (CT) which will modify the displayed virtual sets without intervention of the therapist. Developed in 3ds Max® software, the CT is composed of scenarios and objects that are in the habit of marijuana and cocaine dependent individual's daily life. The interaction with the environment is accomplished using a Human-Computer Interface (HCI) that converts incoming physiological signals indicating anxiety state into commands that change the scenes. Anxiety was characterized by the average variability from cardiac and respiratory rate of 30 volunteers submitted stress environment situations. To evaluate the effectiveness of cue reactivity a total of 50 volunteers who were marijuana, cocaine or both dependent were accompanied. Prior to CT, the results demonstrated a poor correlation between the therapists' predictions and those of the chemically dependent individuals. After exposure to the CT, there was a significant increase of 73% in awareness of the risks of relapse. We confirmed the hypothesis that the CT, controlled only by physiological signals, increases the perception of vulnerability to risk situations of individuals with dependence on marijuana, cocaine or both. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Effects of the fluid flows on enzymatic chemical oscillations

Science.gov (United States)

Shklyaev, Oleg; Yashin, Victor; Balazs, Anna

2017-11-01

Chemical oscillations are ubiquitous in nature and have a variety of promising applications. Usually, oscillating chemical systems are analyzed within the context of a reaction-diffusion framework. Here, we examine how fluid flows carrying the reactants can be utilized to modulate the negative feedback loops and time delays that promote chemical oscillations. We consider a model where a chemical reaction network involves two species, X and Y, which undergo transformations catalyzed by respective enzymes immobilized at the bottom wall of a fluid-filled microchamber. The reactions with the enzymes provide a negative feedback in the chemically oscillating system. In particular, the first enzyme, localized on the first patch, promotes production of chemical X, while the second enzyme, immobilized on the second patch, promotes production of chemical Y, which inhibits the production of chemical X. The separation distance between the enzyme-coated patches sets the time delay required for the transportation of X and Y. The chemical transport is significantly enhanced if convective fluxes accompany the diffusive ones. Therefore, the parameter region where oscillations are present is modified. The findings provide guidance to designing micro-scale chemical reactors with improved functionalities.

Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

Energy Technology Data Exchange (ETDEWEB)

Gray, S.K. [Argonne National Laboratory, IL (United States)

1993-12-01

A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

Reactivation of slow-moving landslides by earthquakes, kinematics measurements and mechanical implications

Science.gov (United States)

Lacroix, Pascal; Perfettini, Hugo; Berthier, Etienne; Taipe, Edu; Guillier, Bertrand

2015-04-01

Major earthquakes in mountainous areas often trigger landslides. The impact of earthquakes on slow-moving landslides is however not well constrained due to few co-seismic measurements of landslide motion. We document the first time-series of a landslide reactivation by an earthquake (Mw6.0, distance 20 km), using continuous GPS measurements over the Maca landslide (Peru). Our survey shows a coseismic response of the landslide of about 2 cm, followed by a relaxation period of 5 weeks during which postseismic slip is three times greater than the coseismic displacement itself. Our results confirm the coseismic activation of landslides and provide the first observation of a post seismic displacement. Finally, a multi-temporal survey using images from the very high resolution Pléiades optical satellite, allowed us to detect 9 active slow-moving landslides over the whole valley. Their pattern of motion show they have been reactivated by the same earthquake. We analyze this small but comprehensive database of landslides reactivated by the earthquake. We find that the landslide motion due to the earthquake is function of the shaking intensity, suggesting a friction at the basal interface dependent on the earthquake solicitation. These various observations are consistent with a mechanical model where slip on the landslide basal interface is governed by rate and state friction, analogous to the mechanics of creeping tectonic faults.

Quick Look Report for Chemical Reactivity Modeling of Various Multi-Canister Overpack Breaches

International Nuclear Information System (INIS)

Bratton, Robert Lawrence

2002-01-01

. A uranium oxide coating covers the exposed uranium metal, yet uranium hydride can still form under the protective oxide coating over the 40-year interim storage time span. The current treatment process at Hanford does not remove chemically bound water contained in the hydrates or in the waters of hydration. The chemically bound water is the source material for hydrogen production over the 40-year storage time. So, additional uranium hydride creates concerns that breaches of an MCO with the appropriate size openings could result in the onset of bulk uranium oxidation with the potential of a self-sustaining thermal excursion or pyrophoric event. For this analysis, the worst-case scenario appears to be the match head configuration in a vertically standing MCO, where all the reactive surface area is placed on the tips of the fuel elements. This configuration concentrates the heat-producing chemical reaction at the tips of the fuel elements. Because no mechanistic drop analysis has been performed at this time to determine the MCO failure modes, parametric breach configurations were chosen in this analysis to determine the MCOs external thermal response range. The first breach is a pair of holes that suddenly open in the MCO wall. This thermal excursion is controlled by the ''thermal chimney effect'' in the 4.27-m (14-ft) tall canisters caused by the multiple holes breach (one high and one low). A second breach where the MCO lid is suddenly removed and exposed to the ambient air environment is evaluated. This thermal excursion is controlled by the countercurrent flow through the top of the MCO. Computer models for these breach configurations were constructed and executed

Multi-scales modeling of reactive transport mechanisms. Impact on petrophysical properties during CO2 storage

International Nuclear Information System (INIS)

Varloteaux, C.

2012-01-01

The geo-sequestration of carbon dioxide (CO 2 ) is an attractive option to reduce the emission of greenhouse gases. Within carbonate reservoirs, acidification of brine in place can occur during CO 2 injection. This acidification leads to mineral dissolution which can modify the transport properties of a solute in porous media. The aim of this study is to quantify the impact of reactive transport on a solute distribution and on the structural modification induced by the reaction from the pore to the reservoir scale. This study is focused on reactive transport problem in the case of single phase flow in the limit of long time. To do so, we used a multi-scale up-scaling method that takes into account (i) the local scale, where flow, reaction and transport are known; (ii) the pore scale, where the reactive transport is addressed by using averaged formulation of the local equations; (iii) the Darcy scale (also called core scale), where the structure of the rock is taken into account by using a three-dimensions network of pore-bodies connected by pore-throats; and (iv) the reservoir scale, where physical phenomenon, within each cell of the reservoir model, are taken into account by introducing macroscopic coefficients deduced from the study of these phenomenon at the Darcy scale, such as the permeability, the apparent reaction rate, the solute apparent velocity and dispersion. (author)

A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

Directory of Open Access Journals (Sweden)

M. De Lucia

2015-02-01

Full Text Available Fully coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i that the presence of CO2 is the only driving force for chemical reactions and (ii that its migration in the reservoir is only marginally affected by immobilisation due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany, both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is shown to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g. by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids of the order of millions of elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

National Research Council Canada - National Science Library

Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B

2002-01-01

Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...

Le Châtelier's conjecture: Measurement of colloidal eigenstresses in chemically reactive materials

Science.gov (United States)

Abuhaikal, Muhannad; Ioannidou, Katerina; Petersen, Thomas; Pellenq, Roland J.-M.; Ulm, Franz-Josef

2018-03-01

Volume changes in chemically reactive materials, such as hydrating cement, play a critical role in many engineering applications that require precise estimates of stress and pressure developments. But a means to determine bulk volume changes in the absence of other deformation mechanisms related to thermal, pressure and load variations, is still missing. Herein, we present such a measuring devise, and a hybrid experimental-theoretical technique that permits the determination of colloidal eigenstresses. Applied to cementitious materials, it is found that bulk volume changes in saturated cement pastes at constant pressure and temperature conditions result from a competition of repulsive and attractive phenomena that originate from the relative distance of the solid particles - much as Henry Louis Le Châtelier, the father of modern cement science, had conjectured in the late 19th century. Precipitation of hydration products in confined spaces entails a repulsion, whereas the concurrent reduction in interparticle distance entails activation of attractive forces in charged colloidal particles. This cross-over from repulsion to attraction can be viewed as a phase transition between a liquid state (below the solid percolation) and the limit packing of hard spheres, separated by an energy barrier that defines the temperature-dependent eigenstress magnitude.

The understanding of the R7T7 glass blocks long term behavior: chemical and transport coupling in fractured media

International Nuclear Information System (INIS)

Chomat, L.

2008-04-01

The long term behavior of nuclear waste glass blocks depends highly on chemical reactions which occur at the surface in contact with water. Studies carried out on inactive fractured glass blocks show that fracture networks play a significant part in reactive surface area. Nevertheless, the complexity of results interpretation, due to a weak knowledge of fracture networks and local lixiviation conditions, does not allow us to comprehend the physical and chemical mechanisms involved. Model cracks are a key step to study chemical and transport coupling in fractured media. Crack lixiviation in aggressive conditions (pH≥11) show that the crack's position (horizontal or vertical) determines the dominant transport mechanism (respectively diffusion or convection induced by gravity). This gravity driven flow seems to be negligible in lower pH conditions. The convective velocity is estimated by a 1D model of reactive transport. Two other parameters are studied: the influence of thermal gradient and the influence of interconnected cracks on alteration. A strong retroactive effect of convection, due to thermal gradient, on the alteration kinetic is observed inside the crack. These works lead to a complete alteration experiment of a 163 crack network subject to a thermal gradient. The use of the geochemical software, HYTEC, within the framework of this study shows the potential of the software which is however limited by the kinetics law used. (author)

Subsurface Transport Over Reactive Multiphases (STORM): A Parallel, Coupled, Nonisothermal Multiphase Flow, Reactive Transport, and Porous Medium Alteration Simulator, Version 3.0

International Nuclear Information System (INIS)

Bacon, Diana H.; White, Mark D.; McGrail, B PETER

2004-01-01

The U.S. Department of Energy must approve a performance assessment (PA) to support the design, construction, approval, and closure of disposal facilities for immobilized low-activity waste (ILAW) currently stored in underground tanks at Hanford, Washington. A critical component of the PA is to provide quantitative estimates of radionuclide release rates from the engineered portion of the disposal facilities. Computer simulations are essential for this purpose because impacts on groundwater resources must be projected to periods of 10,000 years and longer. The computer code selected for simulating the radionuclide release rates is the Subsurface Transport Over Reactive Multiphases (STORM) simulator. The STORM simulator solves coupled conservation equations for component mass and energy that describe subsurface flow over aqueous and gas phases through variably saturated geologic media. The resulting flow fields are used to sequentially solve conservation equations for reactive aqueous phase transport through variably saturated geologic media. These conservation equations for component mass, energy, and solute mass are partial differential equations that mathematically describe flow and transport through porous media. The STORM simulator solves the governing-conservation equations and constitutive functions using numerical techniques for nonlinear systems. The partial differential equations governing thermal and fluid flow processes are solved by the integral volume finite difference method. These governing equations are solved simultaneously using Newton-Raphson iteration. The partial differential equations governing reactive solute transport are solved using either an operator split technique where geochemical reactions and solute transport are solved separately, or a fully coupled technique where these equations are solved simultaneously. The STORM simulator is written in the FORTRAN 77 language, following American National Standards Institute (ANSI) standards

Nondestructive Reactivation of Chemical Protective Garments

National Research Council Canada - National Science Library

Chang, Kuo

1995-01-01

.... Complete reactivation was achieved when the aqueous/ i-propanol/ iodine displacement method of Manes, which removed all but pure hydrocarbon oil soils from the current overgarment Type III foam...

Use of Reactive Distillation for Biodiesel Production: A Literature Survey

Directory of Open Access Journals (Sweden)

Muhammad Dani Supardan

2006-06-01

Full Text Available Biodiesel has been shown to be the best substitute for fossil-based fuels to its environmental advantages and renewable resource availability. There is a great demand for the commercialization of biodiesel production, which in turn calls for a technically and economically reactor technology. The production of biodiesel in existing batch and continuous-flow processes requires excess alcohol, typically 100%, over the stoichiometric molar requirement in order to drive the chemical reaction to completion. In this study, a novel reactor system using a reactive distillation (RD technique was discussed for biodiesel production. RD is a chemical unit operation in which chemical reactions and separations occur simultaneously in one unit. It is an effective alternative to the classical combination of reactor and separation units especially when involving reversible or consecutive chemical reactions such as transesterication process in biodiesel production.

Specific features of the flow structure in a reactive type turbine stage

Science.gov (United States)

Chernikov, V. A.; Semakina, E. Yu.

2017-04-01

The results of experimental studies of the gas dynamics for a reactive type turbine stage are presented. The objective of the studies is the measurement of the 3D flow fields in reference cross sections, experimental determination of the stage characteristics, and analysis of the flow structure for detecting the sources of kinetic energy losses. The integral characteristics of the studied stage are obtained by averaging the results of traversing the 3D flow over the area of the reference cross sections before and behind the stage. The averaging is performed using the conservation equations for mass, total energy flux, angular momentum with respect to the axis z of the turbine, entropy flow, and the radial projection of the momentum flux equation. The flow parameter distributions along the channel height behind the stage are obtained in the same way. More thorough analysis of the flow structure is performed after interpolation of the experimentally measured point parameter values and 3D flow velocities behind the stage. The obtained continuous velocity distributions in the absolute and relative coordinate systems are presented in the form of vector fields. The coordinates of the centers and the vectors of secondary vortices are determined using the results of point measurements of velocity vectors in the cross section behind the turbine stage and their subsequent interpolation. The approach to analysis of experimental data on aerodynamics of the turbine stage applied in this study allows one to find the detailed space structure of the working medium flow, including secondary coherent vortices at the root and peripheral regions of the air-gas part of the stage. The measured 3D flow parameter fields and their interpolation, on the one hand, point to possible sources of increased power losses, and, on the other hand, may serve as the basis for detailed testing of CFD models of the flow using both integral and local characteristics. The comparison of the numerical and

Reactive sputter deposition of boron nitride

International Nuclear Information System (INIS)

Jankowski, A.F.; Hayes, J.P.; McKernan, M.A.; Makowiecki, D.M.

1995-10-01

The preparation of fully dense, boron targets for use in planar magnetron sources has lead to the synthesis of Boron Nitride (BN) films by reactive rf sputtering. The deposition parameters of gas pressure, flow and composition are varied along with substrate temperature and applied bias. The films are characterized for composition using Auger electron spectroscopy, for chemical bonding using Raman spectroscopy and for crystalline structure using transmission electron microscopy. The deposition conditions are established which lead to the growth of crystalline BN phases. In particular, the growth of an adherent cubic BN coating requires 400--500 C substrate heating and an applied -300 V dc bias

Parameters estimation for reactive transport: A way to test the validity of a reactive model

Science.gov (United States)

Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

Modeling reaction histories to study chemical pathways in condensed phase detonation

International Nuclear Information System (INIS)

Scott Stewart, D.; Hernández, Alberto; Lee, Kibaek

2016-01-01

The estimation of pressure and temperature histories, which are required to understand chemical pathways in condensed phase explosives during detonation, is discussed. We argue that estimates made from continuum models, calibrated by macroscopic experiments, are essential to inform modern, atomistic-based reactive chemistry simulations at detonation pressures and temperatures. We present easy to implement methods for general equation of state and arbitrarily complex chemical reaction schemes that can be used to compute reactive flow histories for the constant volume, the energy process, and the expansion process on the Rayleigh line of a steady Chapman-Jouguet detonation. A brief review of state-of-the-art of two-component reactive flow models is given that highlights the Ignition and Growth model of Lee and Tarver [Phys. Fluids 23, 2362 (1980)] and the Wide-Ranging Equation of State model of Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. We discuss evidence from experiments and reactive molecular dynamic simulations that motivate models that have several components, instead of the two that have traditionally been used to describe the results of macroscopic detonation experiments. We present simplified examples of a formulation for a hypothetical explosive that uses simple (ideal) equation of state forms and detailed comparisons. Then, we estimate pathways computed from two-component models of real explosive materials that have been calibrated with macroscopic experiments.

Chemical stability of reactive skin decontamination lotion (RSDL®).

Science.gov (United States)

Bogan, R; Maas, H J; Zimmermann, T

2018-09-01

Reactive Skin Decontamination Lotion (RSDL ® ) is used for the decontamination of Chemical Warfare Agents and Toxic Industrial Compounds after dermal exposure. It has to be stockpiled over a long period and is handled in all climatic zones. Therefore stability is an essential matter of concern. In this work we describe a study to the chemical stability of RSDL ® as basis for an estimation of shelf life. We analysed RSDL ® for the active ingredient 2,3-butandione monoxime (diacetylmonooxime, DAM), the putative degradation product dimethylglyoxime (DMG) and unknown degradation products by means of a reversed phase high pressure liquid chromatography (HPLC). Calculations were done according to the Arrhenius equation. Based on the temperature dependent rate constants, the time span was calculated, until defined threshold values for DAM and DMG subject to specification and valid regulations were exceeded. The calculated data were compared to the ones gathered from stockpiled samples and samples exposed during foreign mission. The decline of DAM followed first order kinetics, while formation of DMG could be described by zero order kinetics. The rate constants were distinctively temperature dependent. Calculated data were in good accordance to the measured ones from stockpile and mission. Based on a specified acceptable DAM-content of 90% and a valid threshold value of 0.1% (w/w) for the degradation product DMG, RSDL ® proved to be stable for at least four years if stored at the recommended conditions of 15°C-30°C. If continuously stored at higher temperatures shelf life will decrease markedly. Therefore RSDL ® is an object for risk orientated quality monitoring during storage. Copyright © 2017 Elsevier B.V. All rights reserved.

General constraints on the effect of gas flows in the chemical evolution of galaxies

International Nuclear Information System (INIS)

Edmunds, M.G.

1990-01-01

The basic equations for the chemical evolution of galaxies in which the 'simple' closed box model is modified to allow any form of inflow or outflow are examined. It is found that there are quite general limiting constraints on the effects that such flows can have. Some implications for the actual chemical evolution of galaxies are discussed, and the constraints should also be useful in understanding the behaviour of detailed numerical models of galactic chemical evolution involving gas flows. (author)

Framing the performance of heat absorption/generation and thermal radiation in chemically reactive Darcy-Forchheimer flow

Directory of Open Access Journals (Sweden)

T. Hayat

Full Text Available The present work aims to report the consequences of heterogeneous-homogeneous reactions in Darcy-Forchheimer flow of Casson material bounded by a nonlinear stretching sheet of variable thickness. Nonlinear stretched surface with variable thickness is the main agent for MHD Darcy-Forchheimer flow. Impact of thermal radiation and non-uniform heat absorption/generation are also considered. Flow in porous space is characterized by Darcy-Forchheimer flow. It is assumed that the homogeneous process in ambient fluid is governed by first order kinetics and the heterogeneous process on the wall surface is given by isothermal cubic autocatalator kinetics. The governing nonlinear ordinary differential equations are solved numerically. Effects of physical variables such as thickness, Hartman number, inertia and porous, radiation, Casson, heat absorption/generation and homogeneous-heterogeneous reactions are investigated. The variations of drag force (skin friction and heat transfer rate (Nusselt numberfor different interesting variables are plotted and discussed. Keywords: Casson fluid, Variable sheet thickness, Darcy-Forchheimer flow, Homogeneous-heterogeneous reactions, Heat generation/absorption, Thermal radiation

Application of chemical methods to assess the mechanism of alkali activation in low calcium fly ash

Energy Technology Data Exchange (ETDEWEB)

Arjunan, P.; Silsbee, M.R.; Roy, D.M. [Pennsylvania State Univ., PA (United States). Materials Research Lab.

1999-11-01

A better understanding of the amount of fly ash unreacted remaining after alkali activation of low calcium fly ash is necessary for elucidating the underlying alkali activation mechanism. An approach to this determination is reported in this study which utilizes an ethylenediamine tetraacetic acid/triethanolamine/NaOH mixture to determine the unreacted fly ash particles present in an OPC-low calcium fly ash mixture, with and without alkali activation. This study also uses another chemical technique called orthophosphoric acid dissolution method to assess the amount of unreacted crystalline phases present in hydrated OPC-ash mixtures at different ages of hydration. The information obtained from these two chemical techniques was used to identify the nature of unreacted fly ash particles present in the hydrated samples. The amount of unreacted fly ash and the compressive strength data were correlated to assess the extent of influence of alkali activation on the reactivity of the amorphous and crystalline phase content of the low calcium fly ash.

Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

Science.gov (United States)

Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

2015-07-23

The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

Material Cycles and Chemicals: Dynamic Material Flow Analysis of Contaminants in Paper Recycling

DEFF Research Database (Denmark)

Pivnenko, Kostyantyn; Laner, David; Astrup, Thomas Fruergaard

2016-01-01

material source-segregation and collection was the least effective strategy for reducing chemical contamination, if the overall recycling rates should be maintained at the current level (approximately 70% for Europe). The study provides a consistent approach for evaluating contaminant levels in material......This study provides a systematic approach for assessment of contaminants in materials for recycling. Paper recycling is used as an illustrative example. Three selected chemicals, bisphenol A (BPA), diethylhexyl phthalate (DEHP) and mineral oil hydrocarbons (MOHs), are evaluated within the paper...... cycle. The approach combines static material flow analysis (MFA) with dynamic material and substance flow modeling. The results indicate that phasing out of chemicals is the most effective measure for reducing chemical contamination. However, this scenario was also associated with a considerable lag...

Corrosion resistance of ZrNxOy thin films obtained by rf reactive magnetron sputtering

International Nuclear Information System (INIS)

Ariza, E.; Rocha, L.A.; Vaz, F.; Cunha, L.; Ferreira, S.C.; Carvalho, P.; Rebouta, L.; Alves, E.; Goudeau, Ph.; Riviere, J.P.

2004-01-01

The main aim of this work is the investigation of the corrosion resistance of single layered zirconium oxynitride, ZrN x O y , thin films in artificial sweat solution at ambient temperature. The films were produced by rf reactive magnetron sputtering, using a pure Zr target at a constant temperature of 300 deg. C. Two different sets of samples were produced. In the first set of films, the substrate bias voltage was the main variable, whereas in the second set, the flow rate of reactive gases (oxygen/nitrogen ratio) was varied. The control of the amount of oxygen allowed the film properties to be tailored from those of covalent zirconium nitride to those of the correspondent ionic oxide. The corrosion behaviour was evaluated by potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) tests. The analysis of EIS data provided detailed information of the corrosion processes occurring at the surface of the system throughout the immersion time. The modifications of the coating microstructure and/or chemical composition induced by the variation of the deposition parameters were also evaluated and correlated with the corrosion mechanisms occurring in each system

Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse: Chapter 12

Science.gov (United States)

Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

2009-01-01

Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

Topological Fluid Mechanics with Applications to Free Surfaces and Axisymmetric Flows

DEFF Research Database (Denmark)

Brøns, Morten

1996-01-01

Topological fluid mechanics is the study of qualitative features of fluid patterns. We discuss applications to the flow beneath a stagnant surface film, and to patterns in axisymmetric flow.......Topological fluid mechanics is the study of qualitative features of fluid patterns. We discuss applications to the flow beneath a stagnant surface film, and to patterns in axisymmetric flow....

A coupled implicit method for chemical non-equilibrium flows at all speeds

Science.gov (United States)

Shuen, Jian-Shun; Chen, Kuo-Huey; Choi, Yunho

1993-01-01

The present time-accurate coupled-solution procedure addresses the chemical nonequilibrium Navier-Stokes equations over a wide Mach-number range uses, in conjunction with the strong conservation form of the governing equations, five unknown primitive variables. The numerical tests undertaken address steady convergent-divergent nozzle flows with air dissociation/recombination, dump combustor flows with n-pentane/air chemistry, and unsteady nonreacting cavity flows.

Mechanism of reactivation of the UV-inactivated cells of Escherichia coli by cell extracts of propionic acid bacteria

International Nuclear Information System (INIS)

Vorob'eva, L.I.; Khodzhaev, E.Y.; Ponomareva, G.M.

1995-01-01

Two mechanisms of reactivation of UV-inactivated Escherichia coli cells - photoreactivation (PhR) and reactivation by the dialyzate of cell extract of propionic acid bacteria - are shown to be different but not completely additive. PhR displays an insignificant negative effect on the reactivaton by active substances (peptides) of the dialyzate, whereas reactivation by dialyzate inhibits PhR. The maximal reactivation can be attained under complete PhR followed by the protective action of dialyzate. The dialyzate protects UV-irradiated E. coli cells with PolA, UvrA, and RecA mutations and Salmonella typhimurium TA 100 (UvrB) cells, and also exerts an antimutagenic effect on S. typhimurium TA 100. Protection by dialyzate is suggested to be due to restoration of the cell division mechanism damaged by UV irradiation. 14 refs., 3 figs., 5 tabs

Molar exergy and flow exergy of pure chemical fuels

International Nuclear Information System (INIS)

Zanchini, Enzo; Terlizzese, Tiziano

2009-01-01

Expressions of the molar exergy and of the molar flow exergy of a pure chemical fuel are deduced rigorously from the basic principles of thermodynamics. It is shown that molar exergy and molar flow exergy coincide when the temperature T and the pressure p of the fuel are equal to the temperature T B and the pressure p B of the environment; a general relation between exergy and flow exergy is proved as a consequence. The deduction of the expression of the molar exergy of a chemical fuel for non-standard values of T B and p B is clarified. For hydrogen, carbon dioxide and several hydrocarbons, tables are reported to allow a simple calculation of the molar exergy of the fuel for any value of the temperature T B and the relative humidity φ B of the environment, in the range 268.15 K ≤ T B ≤ 313.15 K and 0.1 ≤ φ B ≤ 1, with reference to the standard atmospheric pressure. Additional tables are provided to evaluate the difference between the exergy or the flow exergy of the fuel in its given initial state and the exergy at T = T B and p = p B . In these tables, it is assumed that fuel and environment have the same temperature and that the fuel pressure varies in the range 1.01325 bar ≤ p ≤ 200 bar; the fuel may be gas or liquid.

Continuous-Flow Processes in Heterogeneously Catalyzed Transformations of Biomass Derivatives into Fuels and Chemicals

Directory of Open Access Journals (Sweden)

Antonio A. Romero

2012-07-01

Full Text Available Continuous flow chemical processes offer several advantages as compared to batch chemistries. These are particularly relevant in the case of heterogeneously catalyzed transformations of biomass-derived platform molecules into valuable chemicals and fuels. This work is aimed to provide an overview of key continuous flow processes developed to date dealing with a series of transformations of platform chemicals including alcohols, furanics, organic acids and polyols using a wide range of heterogeneous catalysts based on supported metals, solid acids and bifunctional (metal + acidic materials.

Elimination of self-reactive CD8+, but not CD4+, T cells by a peripheral immune mechanism

International Nuclear Information System (INIS)

Rammensee, H.G.; Huegin, D.

1990-01-01

Unirradiated (BALB/c X B6)F1 recipients of lymphocytes from either parent or (B6 X DBA/2)F2 recipients of DBA/2 parental lymphocytes specifically remove the function of donor-derived F1-reactive CTL from the spleen, since such cells could not be recovered 1 week after injection. However, donor-derived CTL specific for third-party antigens, as well as donor-derived F1-reactive CD4+ T cells could be recovered. In contrast, CTL in spleens from recipients sublethally irradiated prior to injections consisted predominantly of F1-reactive CTL in all strain combinations tested. Athymic BALB/c nude mice grafted with fetal thymus of B6 develop a T cell compartment tolerant of BALB/c and B6, like (BALB/c X B6)F1 animals. However, unlike the F1 mice, the thymus-grafted nude mice were not able to eliminate B6-reactive lymphocytes after injection of normal BALB/c spleen cells. Our data indicate the existence of a peripheral immune mechanism capable of selectively eliminating self-reactive CD8+ CTL, but not CD4+, T cells. This mechanism requires self antigen expressed on radiosensitive cells. The presence of T cells tolerant to self antigen by thymic negative selection is not sufficient and perhaps not required. Most likely, this mechanism is involved in the relative resistance to lethal GVHR mediated by parental CD8+ T cells in parent-into-F1 situations

Assessing preferential flow by simultaneously injecting nanoparticle and chemical tracers

KAUST Repository

Subramanian, S. K.; Li, Yan; Cathles, L. M.

2013-01-01

The exact manner in which preferential (e.g., much faster than average) flow occurs in the subsurface through small fractures or permeable connected pathways of other kinds is important to many processes but is difficult to determine, because most chemical tracers diffuse quickly enough from small flow channels that they appear to move more uniformly through the rock than they actually do. We show how preferential flow can be assessed by injecting 2 to 5 nm carbon particles (C-Dots) and an inert KBr chemical tracer at different flow rates into a permeable core channel that is surrounded by a less permeable matrix in laboratory apparatus of three different designs. When the KBr tracer has a long enough transit through the system to diffuse into the matrix, but the C-Dot tracer does not, the C-Dot tracer arrives first and the KBr tracer later, and the separation measures the degree of preferential flow. Tracer sequestration in the matrix can be estimated with a Peclet number, and this is useful for experiment design. A model is used to determine the best fitting core and matrix dispersion parameters and refine estimates of the core and matrix porosities. Almost the same parameter values explain all experiments. The methods demonstrated in the laboratory can be applied to field tests. If nanoparticles can be designed that do not stick while flowing through the subsurface, the methods presented here could be used to determine the degree of fracture control in natural environments, and this capability would have very wide ranging value and applicability.

Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives’ allergenicity

International Nuclear Information System (INIS)

Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H.; Siegel, Paul D.

2016-01-01

Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking.

Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives’ allergenicity

Science.gov (United States)

Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H.; Siegel, Paul D.

2015-01-01

Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking. PMID:26612505

Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

NARCIS (Netherlands)

Duvigneau, Joost; Cornelissen, Stijn; Bardajı´Valls, Nuria; Schönherr, Holger; Vancso, Gyula J.

2009-01-01

Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at

Numerical prediction of flow and mixing characteristics in CVCS chemical addition system

International Nuclear Information System (INIS)

Chang, K.S.

1999-01-01

A numerical result of the flow and mixing characteristics is presented for the flow field created by water injected into a cylindrical tank with an initially stationary fluid. The flow is relevant to the operation of the chemical addition system in the chemical and volume control system (CVCS) of nuclear power plants. This study was undertaken to provide a basis for modification of the previous design which gave a number of difficulties in installation and operation of the chemical addition system because it needs a special reciprocating pump with a high actual head. For the tank of length-to-diameter ratios (L/D) of 1, 2 and 3, each with and without a baffle inside, calculation results were obtained by solving the unsteady laminar two-dimensional elliptic forms of governing equations for the mass, momentum and species concentration. Finite-difference method was used to obtain discretization equations, and the SIMPLER solution algorithm was employed for the calculation procedure. Results showed that the baffle was very effective in enhancing the mixing in the tank, and that a baffle should be installed near the tank entrance in order to inject chemicals into the reactor coolant system (RCS) within the operating time required. (orig.)

Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

International Nuclear Information System (INIS)

Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

2013-01-01

In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called “interphase” between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC–TiC) n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC–TiC) n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

Science.gov (United States)

Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

2013-06-01

In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called "interphase" between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC-TiC)n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC-TiC)n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

Acceptance of low-flow mechanical ventilation in dwellings

International Nuclear Information System (INIS)

Mueller, V.; Peters, M.; Gubler, M.; Maillard, S.; Keller, L.

2001-01-01

This report presents the findings of a survey carried out on the acceptance of 'low-flow mechanical ventilation' (a fan-assisted balanced ventilation with heat recovery) for houses and apartments in Switzerland. The results were obtained on the one hand by reviewing and analysing articles appearing on the subject in the professional and daily press and by telephone interviews with 100 randomly chosen architects and 100 investors in the German and French-speaking parts of Switzerland on the other. These survey participants were asked to express their views on low-flow mechanical ventilation and experience already gained in this area. Further Interviews with tenants, 150 of whom lived in buildings fitted with low-flow mechanical ventilation and 300 in dwellings without this form of ventilation, provided information on the attitude of those directly affected, their satisfaction with the systems or their wishes. The report analyses the results of the surveys and proposes a plan of action to improve information and training for architects, owners and tenants

Technology of combined chemical-mechanical fabrication of durable coatings

Science.gov (United States)

Smolentsev, V. P.; Ivanov, V. V.; Portnykh, A. I.

2018-03-01

The article presents the scientific fundamentals of methodology for calculating the modes and structuring the technological processes of combined chemical-mechanical fabrication of durable coatings. It is shown that they are based on classical patterns, describing the processes of simultaneous chemical and mechanical impact. The paper demonstrates the possibility of structuring a technological process, taking into account the systematic approach to impact management and strengthening the reciprocal positive influence of each impact upon the combined process. The combined processes have been planned for fabricating the model types of chemical-mechanical coatings of durable products in machine construction. The planning methodology is underpinned by a scientific hypothesis of a single source of impact management through energy potential of process components themselves, or by means of external energy supply through mechanical impact. The control of it is fairly thoroughly studied in the case of pulsed external strikes of hard pellets, similar to processes of vibroimpact hardening, thoroughly studied and mastered in many scientific schools of Russia.

A model for chemically-induced mechanical loading on MEMS

DEFF Research Database (Denmark)

Amiot, Fabien

2007-01-01

The development of full displacement field measurements as an alternative to the optical lever technique to measure the mechanical response for microelectro-mechanical systems components in their environment calls for a modeling of chemically-induced mechanical fields (stress, strain, and displac......The development of full displacement field measurements as an alternative to the optical lever technique to measure the mechanical response for microelectro-mechanical systems components in their environment calls for a modeling of chemically-induced mechanical fields (stress, strain...... of the system free energy and its dependence on the surface amount. It is solved in the cantilever case thanks to an asymptotic analysis, and an approached closed-form solution is obtained for the interfacial stress field. Finally, some conclusions regarding the transducer efficiency of cantilevers are drawn...

Mechanisms of current flow in metal-semiconductor ohmic contacts

International Nuclear Information System (INIS)

Blank, T. V.; Gol'dberg, Yu. A.

2007-01-01

Published data on the properties of metal-semiconductor ohmic contacts and mechanisms of current flow in these contacts (thermionic emission, field emission, thermal-field emission, and also current flow through metal shunts) are reviewed. Theoretical dependences of the resistance of an ohmic contact on temperature and the charge-carrier concentration in a semiconductor were compared with experimental data on ohmic contacts to II-VI semiconductors (ZnSe, ZnO), III-V semiconductors (GaN, AlN, InN, GaAs, GaP, InP), Group IV semiconductors (SiC, diamond), and alloys of these semiconductors. In ohmic contacts based on lightly doped semiconductors, the main mechanism of current flow is thermionic emission with the metal-semiconductor potential barrier height equal to 0.1-0.2 eV. In ohmic contacts based on heavily doped semiconductors, the current flow is effected owing to the field emission, while the metal-semiconductor potential barrier height is equal to 0.3-0.5 eV. In alloyed In contacts to GaP and GaN, a mechanism of current flow that is not characteristic of Schottky diodes (current flow through metal shunts formed by deposition of metal atoms onto dislocations or other imperfections in semiconductors) is observed

Investigation of the chemical mechanisms involved in the electropulsation of membranes at the molecular level.

Science.gov (United States)

Breton, Marie; Mir, Lluis M

2018-02-01

The chemical consequences of electropulsation on giant unilamellar vesicles (GUVs), in particular the possible oxidation of unsaturated phospholipids, have been investigated by mass spectrometry, flow cytometry and absorbance methods. Pulse application induced oxidation of the GUV phospholipids and the oxidation level depended on the duration of the pulse. Light and O 2 increased the level of pulse-induced lipid peroxidation whereas the presence of antioxidants either in the membrane or in the solution completely suppressed peroxidation. Importantly, pulse application did not create additional reactive oxygen species (ROS) in GUV-free solution. Lipid peroxidation seems to result from a facilitation of the lipid peroxidation by the ROS already present in the solution before pulsing, not from a direct pulse-induced peroxidation. The pulse would facilitate the entrance of ROS in the core of the membrane, allowing the contact between ROS and lipid chains and provoking the oxidation. Our findings demonstrate that the application of electric pulses on cells could induce the oxidation of the membrane phospholipids since cell membranes contain unsaturated lipids. The chemical consequences of electropulsation will therefore have to be taken into account in future biomedical applications of electropulsation since oxidized phospholipids play a key role in many signaling pathways and diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Understanding "Understanding" Flow for Network-Centric Warfare: Military Knowledge-Flow Mechanics

National Research Council Canada - National Science Library

Nissen, Mark

2002-01-01

Network-centric warfare (NCW) emphasizes information superiority for battlespace efficacy, but it is clear that the mechanics of how knowledge flows are just as important as those pertaining to the networks and communication...

A novel mechanical model for phase-separation in debris flows

Science.gov (United States)

Pudasaini, Shiva P.

2015-04-01

Understanding the physics of phase-separation between solid and fluid phases as a two-phase mass moves down slope is a long-standing challenge. Here, I propose a fundamentally new mechanism, called 'separation-flux', that leads to strong phase-separation in avalanche and debris flows. This new model extends the general two-phase debris flow model (Pudasaini, 2012) to include a separation-flux mechanism. The new flux separation mechanism is capable of describing and controlling the dynamically evolving phase-separation, segregation, and/or levee formation in a real two-phase, geometrically three-dimensional debris flow motion and deposition. These are often observed phenomena in natural debris flows and industrial processes that involve the transportation of particulate solid-fluid mixture material. The novel separation-flux model includes several dominant physical and mechanical aspects that result in strong phase-separation (segregation). These include pressure gradients, volume fractions of solid and fluid phases and their gradients, shear-rates, flow depth, material friction, viscosity, material densities, boundary structures, gravity and topographic constraints, grain shape, size, etc. Due to the inherent separation mechanism, as the mass moves down slope, more and more solid particles are brought to the front, resulting in a solid-rich and mechanically strong frontal surge head followed by a weak tail largely consisting of the viscous fluid. The primary frontal surge head followed by secondary surge is the consequence of the phase-separation. Such typical and dominant phase-separation phenomena are revealed here for the first time in real two-phase debris flow modeling and simulations. However, these phenomena may depend on the bulk material composition and the applied forces. Reference: Pudasaini, Shiva P. (2012): A general two-phase debris flow model. J. Geophys. Res., 117, F03010, doi: 10.1029/2011JF002186.

Microstructure and strain rate effects on the mechanical behavior of particle reinforced epoxy-based reactive materials

Science.gov (United States)

White, Bradley William

The effects of reactive metal particles on the microstructure and mechanical properties of epoxy-based composites is investigated in this work. Particle reinforced polymer composites show promise as structural energetic materials that can provide structural strength while simultaneously being capable of releasing large amounts of chemical energy through highly exothermic reactions occurring between the particles and with the matrix. This advanced class of materials is advantageous due to the decreased amount of high density inert casings needed for typical energetic materials and for their ability to increase payload expectancy and decrease collateral damage. Structural energetic materials can be comprised of reactive particles that undergo thermite or intermetallic reactions. In this work nickel (Ni) and aluminum (Al) particles were chosen as reinforcing constituents due to their well characterized mechanical and energetic properties. Although, the reactivity of nickel and aluminum is well characterized, the effects of their particle size, volume fractions, and spatial distribution on the mechanical behavior of the epoxy matrix and composite, across a large range of strain rates, are not well understood. To examine these effects castings of epoxy reinforced with 20--40 vol.% Al and 0--10 vol.% Ni were prepared, while varying the aluminum nominal particle size from 5 to 50 mum and holding the nickel nominal particle size constant at 50 mum. Through these variations eight composite materials were produced, possessing unique microstructures exhibiting different particle spatial distributions and constituent makeup. In order to correlate the microstructure to the constitutive response of the composites, techniques such as nearest-neighbor distances, and multiscale analysis of area fractions (MSAAF) were used to quantitatively characterize the microstructures. The composites were investigated under quasi-static and dynamic compressive loading conditions to characterize

Mechanisms governing the reactivation-dependent destabilization of memories and their role in extinction

Directory of Open Access Journals (Sweden)

Charlotte Rachael Flavell

2013-12-01

Full Text Available The extinction of learned associations has traditionally been considered to involve new learning, which competes with the original memory for control over behaviour. However, a recent resurgence of interest in reactivation-dependent amnesia has revealed that the retrieval of fear-related memory (with what is essentially a brief extinction session can result in it’s destabilization. This review discusses some of the cellular and molecular mechanisms that are involved in the destabilization of a memory following it’s reactivation and/or extinction, and investigates the evidence that extinction may involve both new learning as well as a partial destabilization-induced erasure of the original memory trace.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 117; Issue 5. Application of localized reactivity index in combination with periodic DFT calculation to rationalize the swelling mechanism of clay type inorganic material. Abhijit Chatterjee. Volume 117 Issue 5 September 2005 pp 533-539 ...

Mechanical and chemical responses of low-velocity impacted RDX and HMX explosive powders

Science.gov (United States)

Wu, Yanqing; Guo, Hongfu; Huang, Fenglei; Bao, Xiaowei; Explosion; damage Team

2017-06-01

The experimental analyses of mechanical and chemical responses of RDX and HMX particles were performed based on the optimized drop-weight experimental system equipped with the High-Speed Camera (HSC). It has been found that Jetting phenomenon observed by HSC is the result of the energy released by gaseous products, which push the pulverized or melted explosives to splash radially. Jetting is the only and the most obvious difference between reactive and inert particles prior to combustion so that jetting can be regarded as the sign of ignition. Area expansion velocity, jetting velocity, and flame propagation velocity have been estimated via image processing, making it possible to characterize mechanical deformation and violence of reaction of each stage. Hot-spots coalescence promotes flame propagation whose velocity reflects the violence of deflagration reaction. Jetting appearance time can be used to determine time-to-ignition more accurately than other ways. For RDX, molten phase plays an important role to the formation of the hot-spots. Multiple particles experienced more severe burning reactions than an individual particle. China National Nature Science Foundation (11572045), ``Science Challenging Program'' (JCKY2016212A501),opening fund from Safety ammunition research and Development Center (RMC2015B03).

Characteristics of flow and reactive pollutant dispersion in urban street canyons

Science.gov (United States)

Park, Soo-Jin; Kim, Jae-Jin; Kim, Minjoong J.; Park, Rokjin J.; Cheong, Hyeong-Bin

2015-05-01

In this study, the effects of aspect ratio defined as the ratio of building height to street width on the dispersion of reactive pollutants in street canyons were investigated using a coupled CFD-chemistry model. Flow characteristics for different aspect ratios were analyzed first. For each aspect ratio, six emission scenarios with different VOC-NOX ratios were considered. One vortex was generated when the aspect ratio was less than 1.6 (shallow street canyon). When the aspect ratio was greater than 1.6 (deep street canyon), two vortices were formed in the street canyons. Comparing to previous studies on two-dimensional street canyons, the vortex center is slanted toward the upwind building and reverse and downward flows are dominant in street canyons. Near the street bottom, there is a marked difference in flow pattern between in shallow and deep street canyons. Near the street bottom, reverse and downward flows are dominant in shallow street canyon and flow convergence exists near the center of the deep street canyons, which induces a large difference in the NOX and O3 dispersion patterns in the street canyons. NOX concentrations are high near the street bottom and decreases with height. The O3 concentrations are low at high NO concentrations near the street bottom because of NO titration. At a low VOC-NOX ratio, the NO concentrations are sufficiently high to destroy large amount of O3 by titration, resulting in an O3 concentration in the street canyon much lower than the background concentration. At high VOC-NOX ratios, a small amount of O3 is destroyed by NO titration in the lower layer of the street canyons. However, in the upper layer, O3 is formed through the photolysis of NO2 by VOC degradation reactions. As the aspect ratio increases, NOX (O3) concentrations averaged over the street canyons decrease (increase) in the shallow street canyons. This is because outward flow becomes strong and NOX flux toward the outsides of the street canyons increases

Impact of microstructure evolution on the difference between geometric and reactive surface areas in natural chalk

Science.gov (United States)

Yang, Y.; Bruns, S.; Stipp, S. L. S.; Sørensen, H. O.

2018-05-01

The coupling between flow and mineral dissolution drives the evolution of many natural and engineered flow systems. Pore surface changes as microstructure evolves but this transient behaviour has traditionally been difficult to model. We combined a reactor network model with experimental, greyscale tomography data to establish the morphological grounds for differences among geometric, reactive and apparent surface areas in dissolving chalk. This approach allowed us to study the effects of initial geometry and macroscopic flow rate independently. The simulations showed that geometric surface, which represents a form of local transport heterogeneity, increases in an imposed flow field, even when the porous structure is chemically homogeneous. Hence, the fluid-reaction coupling leads to solid channelisation, which further results in fluid focusing and an increase in geometric surface area. Fluid focusing decreases the area of reactive surface and the residence time of reactant, both contribute to the over-normalisation of reaction rate. In addition, the growing and merging of microchannels, near the fluid entrance, contribute to the macroscopic, fast initial dissolution rate of rocks.

Fringe-controlled biodegradation under dynamic conditions: Quasi 2-D flow-through experiments and reactive-transport modeling

Science.gov (United States)

Eckert, Dominik; Kürzinger, Petra; Bauer, Robert; Griebler, Christian; Cirpka, Olaf A.

2015-01-01

Biodegradation in contaminated aquifers has been shown to be most pronounced at the fringe of contaminant plumes, where mixing of contaminated water and ambient groundwater, containing dissolved electron acceptors, stimulates microbial activity. While physical mixing of contaminant and electron acceptor by transverse dispersion has been shown to be the major bottleneck for biodegradation in steady-state plumes, so far little is known on the effect of flow and transport dynamics (caused, e.g., by a seasonally fluctuating groundwater table) on biodegradation in these systems. Towards this end we performed experiments in quasi-two-dimensional flow-through microcosms on aerobic toluene degradation by Pseudomonas putida F1. Plume dynamics were simulated by vertical alteration of the toluene plume position and experimental results were analyzed by reactive-transport modeling. We found that, even after disappearance of the toluene plume for two weeks, the majority of microorganisms stayed attached to the sediment and regained their full biodegradation potential within two days after reappearance of the toluene plume. Our results underline that besides microbial growth, also maintenance and dormancy are important processes that affect biodegradation performance under transient environmental conditions and therefore deserve increased consideration in future reactive-transport modeling.

Inline chemical process analysis in micro-plants based on thermoelectric flow and impedimetric sensors

International Nuclear Information System (INIS)

Jacobs, T; Kutzner, C; Hauptmann, P; Kropp, M; Lang, W; Brokmann, G; Steinke, A; Kienle, A

2010-01-01

In micro-plants, as used in chemical micro-process engineering, an integrated inline analytics is regarded as an important factor for the development and optimization of chemical processes. Up to now, there is a lack of sensitive, robust and low-priced micro-sensors for monitoring mixing and chemical conversion in micro-fluidic channels. In this paper a novel sensor system combining an impedimetric sensor and a novel pressure stable thermoelectric flow sensor for monitoring chemical reactions in micro-plants is presented. The CMOS-technology-based impedimetric sensor mainly consists of two capacitively coupled interdigital electrodes on a silicon chip. The thermoelectric flow sensor consists of a heater in between two thermopiles on a perforated membrane. The pulsed and constant current feeds of the heater were analyzed. Both sensors enable the analysis of chemical conversion by means of changes in the thermal and electrical properties of the liquid. The homogeneously catalyzed synthesis of n-butyl acetate as a chemical model system was studied. Experimental results revealed that in an overpressure regime, relative changes of less than 1% in terms of thermal and electrical properties can be detected. Furthermore, the transition from one to two liquid phases accompanied by the change in slug flow conditions could be reproducibly detected

Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

International Nuclear Information System (INIS)

Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.; Murray, Christopher J.; Ward, Anderson L.; Dayvault, Richard; Waichler, Scott R.; Newcomer, Darrell R.; Spane, Frank A.; Long, Philip E.

2011-01-01

Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely through previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after ∼30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been

Biodecolorization and biodegradation of Reactive Blue by ...

African Journals Online (AJOL)

SERVER

2007-06-18

Jun 18, 2007 ... Aspergillus sp. effectively decolorized Reactive Blue and other structurally different synthetic dyes. Agitation was found to be an important ... Few chemically different dyes such as Reactive Black (75%), Reactive Yellow (70%),. Reactive Red (33%) and ..... Degradation of azo dyes by the lignin degrading ...

Responses of human birch pollen allergen-reactive T cells to chemically modified allergens (allergoids).

Science.gov (United States)

Dormann, D; Ebner, C; Jarman, E R; Montermann, E; Kraft, D; Reske-Kunz, A B

1998-11-01

Allergoids are widely used in specific immunotherapy for the treatment of IgE-mediated allergic diseases. The aim of this study was to analyse whether a modification of birch pollen allergens with formaldehyde affects the availability of T-cell epitopes. Efficient modification of the allergens was verified by determining IgE and IgG binding activity using ELISA inhibition tests. T-cell responses to birch pollen allergoids were analysed in polyclonal systems, using peripheral blood mononuclear cells (PBMC) of five birch pollen-allergic individuals, as well as birch pollen extract-reactive T-cell lines (TCL), established from the peripheral blood of 14 birch pollen-allergic donors. To determine whether the modification of natural (n)Bet v 1 with formaldehyde or maleic anhydride results in epitope-specific changes in T-cell reactivities, 22 Bet v 1-specific T-cell clones (TCC), established from nine additional birch pollen-allergic individuals, were tested for their reactivity with these products. The majority of PBMC and TCL showed a reduced response to the birch pollen extract allergoid. Bet v 1-specific TCC could be divided into allergoid-reactive and -non-reactive TCC. No simple correlation between possible modification sites of formaldehyde in the respective T-cell epitopes and the stimulatory potential of the allergoid was observed. Mechanisms of suppression or of anergy induction were excluded as an explanation for the non-reactivity of representative TCC. All TCC could be stimulated by maleylated and unmodified nBet v 1 to a similar extent. These results demonstrate differences in the availability of T-cell epitopes between allergoids and unmodified allergens, which are most likely due to structural changes within the allergen molecule.

Effects of Building‒roof Cooling on Flow and Distribution of Reactive Pollutants in street canyons

Science.gov (United States)

Park, S. J.; Choi, W.; Kim, J.; Jeong, J. H.

2016-12-01

The effects of building‒roof cooling on flow and dispersion of reactive pollutants were investigated in the framework of flow dynamics and chemistry using a coupled CFD‒chemistry model. For this, flow characteristics were analyzed first in street canyons in the presence of building‒roof cooling. A portal vortex was generated in street canyon, producing dominant reverse and outward flows near the ground in all the cases. The building‒roof cooling increased horizontal wind speeds at the building roof and strengthened the downward motion near the downwind building in the street canyon, resultantly intensifying street canyon vortex strength. The flow affected the distribution of primary and secondary pollutants. Concentrations of primary pollutants such as NOx, VOC and CO was high near the upwind building because the reverse flows were dominant at street level, making this area the downwind region of emission sources. Concentration of secondary pollutant such as O3 was lower than the background near the ground, where NOX concentrations were high. Building‒roof cooling decreased the concentration of primary pollutants in contrasted to those under non‒cooling conditions. In contrast, building‒roof cooling increased O3 by reducing NO concentrations in urban street canyon compared to concentrations under non‒cooling conditions.

Chemical exchange effects in spectral line shapes

International Nuclear Information System (INIS)

Diaz, M.A.; Veguillas, J.

1990-01-01

A theory of spectral-line shapes has been extended to the case in which relaxation broadening may be influenced by reactive interactions. This extension is valid for gaseous systems in the same way it is valid for condensed media, and particularly, for such chemical mechanisms as isomerizations. The dependence of the spectral rate on the chemical exchange rate is clarified. Finally, a discussion concerning the above aspects and their applications has been included. (author)

Cerebral blood flow and CO2 reactivity in transient ischemic attacks: comparison between TIAs due to the ICA occlusion and ICA mild stenosis

International Nuclear Information System (INIS)

Tsuda, Y.; Kimura, K.; Yoneda, S.; Etani, H.; Asai, T.; Nakamura, M.; Abe, H.

1983-01-01

Hemispheric mean cerebral blood flow (CBF), together with its CO2 reactivity in response to hyperventilation, was investigated in 18 patients with transient ischemic attacks (TIAs) by intraarterial 133Xe injection method in a subacute-chronic stage of the clinical course. In 8 patients, the lesion responsible for symptoms was regarded as unilateral internal carotid artery (ICA) occlusion, and in 10 patients, it was regarded as unilateral ICA mild stenosis (less than 50% stenosis in diameter). Resting flow values were significantly decreased in the affected hemisphere of TIA due to the ICA occlusion as compared with the unaffected hemisphere of the same patient, regarded as the relative control. It was not decreased in the affected hemisphere of TIA due to the ICA mild stenosis as compared with the control. With respect to the responsiveness of CBF to changes in PaCO2, it was preserved in both TIAs, due to the ICA occlusion and ICA mild stenosis. Vasoparalysis was not observed in either types of TIAs in the subacute-chronic stage. However, in the relationship of blood pressure and CO2 reactivity, expressed as delta CBF(%)/delta PaCO2, pressure-dependent CO2 reactivity as a group was observed with significance in 8 cases of TIA due to the ICA occlusion, while no such relationship was noted in 10 cases of TIA due to the ICA mild stenosis. Moreover, clinical features were different between TIAs due to the ICA occlusion and ICA mild stenosis, i.e., more typical, repeatable TIA (6.3 +/- 3.7 times) with shorter duration (less than 30 minutes) was observed in TIAs due to the ICA mild stenosis, while more prolonged, less repeatable TIA (2.4 +/- 1.4 times) was observed in TIAs due to fixed obstruction of the ICA. From these observations, two different possible mechanisms as to the pathogenesis of TIA might be expected

Final Report: Molecular Mechanisms of Interfacial Reactivity in Near Surface and Extreme Geochemical Environments (DE-SC0009362)

Energy Technology Data Exchange (ETDEWEB)

Dixon, David A [Univ. of Alabama, Tuscaloosa, AL (United States)

2016-03-27

The prediction of the long-term stability and safety of geologic sequestration of greenhouse gases requires a detailed understanding of subsurface transport and chemical interactions between the disposed greenhouse gases and the geologic media. In this regard, mineral-fluid interactions are of prime importance since reactions that occur on or near the interface can assist in the long term sequestration of CO2 by trapping in mineral phases such as carbonates, as well as influencing the subsurface migration of the disposed fluids via creation or plugging of pores or fractures in the host rock strata. Previous research on mineral-fluid interaction for subsurface CO2 storage has focused almost entirely on the aqueous phase, i.e., reactivity with aqueous solutions or brines containing dissolved CO2. However, interactions with neat to water-saturated non-aqueous fluids are of equal if not greater importance since supercritical CO2 (scCO2) is less dense than the aqueous phase or oil which will create a buoyant scCO2 plume that ultimately will dominate the pore volume within the caprock, and the injected scCO2 will contain water soon after injection and this water can be highly reactive. Collectively, therefore, mineral interactions with water-saturated scCO2-dominated fluids are pivotal and could result in the stable sequestration of CO2 by trapping in mineral phases such as metal carbonates within otherwise permeable zones in the caprock. The primary objective is to unravel the molecular mechanisms governing the reactivity of mineral phases important in the geologic sequestration of CO2 with variably wet supercritical carbon dioxide as a function of T, P, and mineral structure using computational chemistry. This work is in close collaboration with the PNNL Geosciences effort. The focus of the work at The University of Alabama is computational studies of the formation of magnesium and calcium carbonates and oxides and their reactivity and providing computational support

Mechanisms of group A Streptococcus resistance to reactive oxygen species.

Science.gov (United States)

Henningham, Anna; Döhrmann, Simon; Nizet, Victor; Cole, Jason N

2015-07-01

Streptococcus pyogenes, also known as group A Streptococcus (GAS), is an exclusively human Gram-positive bacterial pathogen ranked among the 'top 10' causes of infection-related deaths worldwide. GAS commonly causes benign and self-limiting epithelial infections (pharyngitis and impetigo), and less frequent severe invasive diseases (bacteremia, toxic shock syndrome and necrotizing fasciitis). Annually, GAS causes 700 million infections, including 1.8 million invasive infections with a mortality rate of 25%. In order to establish an infection, GAS must counteract the oxidative stress conditions generated by the release of reactive oxygen species (ROS) at the infection site by host immune cells such as neutrophils and monocytes. ROS are the highly reactive and toxic byproducts of oxygen metabolism, including hydrogen peroxide (H2O2), superoxide anion (O2•(-)), hydroxyl radicals (OH•) and singlet oxygen (O2*), which can damage bacterial nucleic acids, proteins and cell membranes. This review summarizes the enzymatic and regulatory mechanisms utilized by GAS to thwart ROS and survive under conditions of oxidative stress. © FEMS 2015.

Flow and nutrient dynamics in a subterranean estuary (Waquoit Bay, MA, USA) : Field data and reactive transport modeling

NARCIS (Netherlands)

Spiteri, C.; Slomp, C.P.; Charette, M.A.; Tuncay, K.; Meile, C.

2008-01-01

A two-dimensional (2D) reactive transport model is used to investigate the controls on nutrient (NO3-, NH4+, PO4) dynamics in a coastal aquifer. The model couples density-dependent flow to a reaction network which includes oxic degradation of organic matter, denitrification, iron oxide reduction,

Modeling of multiphase flow with solidification and chemical reaction in materials processing

Science.gov (United States)

Wei, Jiuan

moving the side insulation layer upward. It is possible to produce high quality crystal with a good combination of heating and cooling. SiC based ceramic materials fabricated by polymer pyrolysis and synthesis becomes a promising candidate for nuclear applications. To obtain high uniformity of microstructure/concentration fuel without crack at high operating temperature, it is important to understand transport phenomena in material processing at different scale levels. In our prior work, a system level model based on reactive porous media theory was developed to account for the pyrolysis process in uranium-ceramic nuclear fabrication In this thesis, a particle level mesoscopic model based on the Smoothed Particle Hydrodynamics (SPH) is developed for modeling the synthesis of filler U3O8 particles and SiC matrix. The system-level model provides the thermal boundary conditions needed in the particle level simulation. The evolution of particle concentration and structure as well as composition of composite produced will be investigated. Since the process temperature and heat flux play the important roles in material quality and uniformity, the effects of heating rate at different directions, filler particle size and distribution on uniformity and microstructure of the final product are investigated. Uncertainty issue is also discussed. For the multiphase flow with directional solidification, a system level based on FVM is established. In this model, melt convection, temperature distribution, phase change and solidification interface can be investigated. For the multiphase flow with chemical reaction, a particle level model based on SPH method is developed to describe the pyrolysis and synthesis process of uranium-ceramic nuclear fuel. Due to its mesh-free nature, SPH can easily handle the problems with multi phases and components, large deformation, chemical reactions and even solidifications. A multi-scale meso-macroscopic approach, which combine a mesoscopic model based

Fluidization mechanisms in slurry flow

Energy Technology Data Exchange (ETDEWEB)

Campbell, C. S.

1989-01-01

There are two mechanisms by which heavy settling particles may be suspended in a horizontal slurry flow: (1) by particle-particle interactions (e.g. Bagnold dispersive stresses) and (2) by particle-fluid interactions (e.g. entrainment of the particles by turbulent eddies.) The purpose of this investigation is to determine to what extent each fluidization mechanism is active and the effect of the fluidization mechanism on the global properties of the slurry. The technique employs the understanding that the particles entrained in the turbulence of the fluid will appear as an increased hydrostatic head across the channel. This may be directly measured and can be related to the fraction of the mass of particles that are supported by fluid-particle forces. (The rest must therefore be supported by particle-particle forces.) 17 refs., 26 figs.

Evaluation of incremental reactivity and its uncertainty in Southern California.

Science.gov (United States)

Martien, Philip T; Harley, Robert A; Milford, Jana B; Russell, Armistead G

2003-04-15

The incremental reactivity (IR) and relative incremental reactivity (RIR) of carbon monoxide and 30 individual volatile organic compounds (VOC) were estimated for the South Coast Air Basin using two photochemical air quality models: a 3-D, grid-based model and a vertically resolved trajectory model. Both models include an extended version of the SAPRC99 chemical mechanism. For the 3-D modeling, the decoupled direct method (DDM-3D) was used to assess reactivities. The trajectory model was applied to estimate uncertainties in reactivities due to uncertainties in chemical rate parameters, deposition parameters, and emission rates using Monte Carlo analysis with Latin hypercube sampling. For most VOC, RIRs were found to be consistent in rankings with those produced by Carter using a box model. However, 3-D simulations show that coastal regions, upwind of most of the emissions, have comparatively low IR but higher RIR than predicted by box models for C4-C5 alkenes and carbonyls that initiate the production of HOx radicals. Biogenic VOC emissions were found to have a lower RIR than predicted by box model estimates, because emissions of these VOC were mostly downwind of the areas of primary ozone production. Uncertainties in RIR of individual VOC were found to be dominated by uncertainties in the rate parameters of their primary oxidation reactions. The coefficient of variation (COV) of most RIR values ranged from 20% to 30%, whereas the COV of absolute incremental reactivity ranged from about 30% to 40%. In general, uncertainty and variability both decreased when relative rather than absolute reactivity metrics were used.

KIVA3, Transient Multicomponent 2-D and 3-D Reactive Flows with Fuel Sprays

International Nuclear Information System (INIS)

Amsden, A.A.

2001-01-01

1 - Description of program or function: KIVA3VRELEASE2 is a computer program for the numerical calculation of transient, two and three-dimensional, chemically reactive flows with sprays. It is a newer version of the earlier KIVA3 (1993) that has now been extended to model vertical of canted valves in the cylinder head of a gasoline or diesel engine. KIVA3, in turn, was based on the earlier KIVA2 (1989) and uses the same numerical solution procedure and solves the same sort of equations. KIVA3VRELEASE2 uses a block-structured mesh with connectivity defined through indirect addressing. The departure from a single rectangular structure in logical space allows complex geometries to be modeled with significantly greater efficiency because large regions of deactivated cells are no longer necessary. Cell-face boundary conditions permit greater flexibility and simplification in the application of boundary conditions. KIVA3VRELEASE2 contains a number of significant changes. New features enhance the robustness, efficiency, and usefulness of the overall program for engine modeling. Automatic restart of the cycle with a reduced time-step in case of iteration limit or temperature overflow will reduce code crashes. A new option provides automatic deactivation of a port region when it is closed from the cylinder and reactivation when it communicates with the cylinder. Corrections in the code improve accuracy; extensions to the particle-based liquid wall film model makes the model more complete and a spli injection option has been added. A new subroutine monitors the liquid and gaseous fuel phases and energy balance data and emissions are monitored and printed. New features have been added to the grid generator K3PREP and the graphics post processor, K3POST. 2 - Method of solution: KIVA3VRELEASE2 solves the unsteady equations of motion of a turbulent, chemically reactive mixture of ideal gases, coupled to the equations for a single-component vaporizing fuel spray. The gas

Mechanical and chemical decontamination of surfaces

International Nuclear Information System (INIS)

Kienhoefer, M.

1982-01-01

Decontamination does not mean more than a special technique of cleaning surfaces by methods well known in the industry. The main difference consists in the facts that more than just the visible dirt is to be removed and that radioactive contamination cannot be seen. Especially, intensive mechanical and chemical carry-off methods are applied to attack the surfaces. In order to minimize damages caused to the surfaces, the decontamination method is to adapt to the material and the required degree of decontamination. The various methods, their advantages and disadvantages are described, and the best known chemical solutions are shown. (orig./RW)

Study on flow characteristics of chemically reacting liquid jet

International Nuclear Information System (INIS)

Hong Seon Dae; Okamoto, Koji; Takata, Takashi; Yamaguchi, Akira

2004-07-01

Tube rupture accidents in steam generators of sodium-cooled fast breeder reactors are important for safety because the rupture may propagates to neighboring tubes due to sodium-water reaction. In order to clarify the thermal-hydraulic phenomena in the accidents, the flow pattern and the interface in multi-phase flow must be investigated. The JNC cooperative research scheme on the nuclear fuel cycle with the University of Tokyo has been carried to develop a simultaneous measurement system of concentration and velocity profiles and to evaluate influence of chemical reaction on mixing phenomena. In the experiments, aqueous liquor of acetic acid and ammonium hydroxide are selected as a simulant fluid instead of liquid sodium and water vapor. The following conclusions are obtained in this research. Laser Induced Fluorescence (LIF) technique was adopted to measure reacting zone and pH distribution in chemically reacting liquid round free jet. As a result, it was found that the chemical reaction, which took place at the interface between the jet and outer flow, suppressed the mixing phenomenon (in 2001 research). Dynamic Particle Image Velocimetry (PIV) method was developed to measure instantaneous velocity profile with high temporal resolution. In the Dynamic PIV, a high-speed video camera coupled with a high-speed laser pulse generator was implemented. A time-line trend of interfacial area in the free jet was investigated with the Dynamic PIV. This technique was also applied to a complicated geometry (in 2002 research). A new algorithms for image analysis was developed to evaluated the Dynamic PIV data in detail. The characteristics of the mixing phenomenon with reacting jet such as the turbulent kinetic energy and the Reynolds stress were estimated in a spatial and temporal spectrum (in 2003 research). (author)

Coupled Thermo-Hydro-Mechanical-Chemical Modeling of Water Leak-Off Process during Hydraulic Fracturing in Shale Gas Reservoirs

Directory of Open Access Journals (Sweden)

Fei Wang

2017-11-01

Full Text Available The water leak-off during hydraulic fracturing in shale gas reservoirs is a complicated transport behavior involving thermal (T, hydrodynamic (H, mechanical (M and chemical (C processes. Although many leak-off models have been published, none of the models fully coupled the transient fluid flow modeling with heat transfer, chemical-potential equilibrium and natural-fracture dilation phenomena. In this paper, a coupled thermo-hydro-mechanical-chemical (THMC model based on non-equilibrium thermodynamics, hydrodynamics, thermo-poroelastic rock mechanics, and non-isothermal chemical-potential equations is presented to simulate the water leak-off process in shale gas reservoirs. The THMC model takes into account a triple-porosity medium, which includes hydraulic fractures, natural fractures and shale matrix. The leak-off simulation with the THMC model involves all the important processes in this triple-porosity medium, including: (1 water transport driven by hydraulic, capillary, chemical and thermal osmotic convections; (2 gas transport induced by both hydraulic pressure driven convection and adsorption; (3 heat transport driven by thermal convection and conduction; and (4 natural-fracture dilation considered as a thermo-poroelastic rock deformation. The fluid and heat transport, coupled with rock deformation, are described by a set of partial differential equations resulting from the conservation of mass, momentum, and energy. The semi-implicit finite-difference algorithm is proposed to solve these equations. The evolution of pressure, temperature, saturation and salinity profiles of hydraulic fractures, natural fractures and matrix is calculated, revealing the multi-field coupled water leak-off process in shale gas reservoirs. The influences of hydraulic pressure, natural-fracture dilation, chemical osmosis and thermal osmosis on water leak-off are investigated. Results from this study are expected to provide a better understanding of the

Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

Directory of Open Access Journals (Sweden)

Hossain eSazzad

2016-05-01

Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

Reactive Transport of Marcellus Shale Waters in Natural Aquifers: the Role of Mineralogical Compositions and Spatial Distribution Patterns

Science.gov (United States)

Cai, Z.; Wen, H.; Li, L.

2017-12-01

Accidental release of Marcellus Shale waters (MSW) can release high concentrations of chemicals that can deteriorate groundwater quality. It is important to understand the reactive transport and fate of chemicals from MSW. Natural aquifers typically have complex mineralogical compositions and are heterogeneous with large spatial variation in terms of physical and geochemical properties. To investigate the effects of mineralogical compositions, flow-through experiments and reactive transport modeling were carried out using 3 large columns (5 cm×50 cm, Quartz, Calcite, and Vermiculite). Results indicate calcite immobilizes heavy metals by precipitation and solid solution partitioning (coprecipitation). Vermiculite retards heavy metals through ion exchange. The sorbed chemicals however slowly release back to the groundwater. Na and Ca transport similarly to Br in Qtz and Cal columns however become sorbed in Vrm column during release through ion exchange by 27.8% and 46.5%, respectively and later slowly release back to aqueous phase. To understand the role of mineral spatial patterns, three 2D flow-cell (40 cm×12 cm×1 cm) experiments were carried out. All flow cells have the same clay mass within quartz matrix but different spatial patterns characterized by the relative length of the clay zone ( 0, ¼, ½) of the domain length (L). Results show that in the uniform column, ion exchange dominates and most Ba sorbs to the solid phase, to an extent Ba cannot precipitate out with SO4 as barite. In 1/2-Zone, however, most Ba precipitates as barite. In 1/4-Zone, both ion exchange and mineral precipitation occur. In general, the 1/2-Zone has the smallest ion exchange capacity for other species including Na, Ca, Mg, K and heavy metals (Mn, Cu, Zn, Cd and Pb) as well. Our flow cell experiment emphasizes the importance of mineral spatial patterns in regulating not only reaction rates but also the type of reactions in controlling the reactive transport of MSW chemicals. The

THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

Science.gov (United States)

In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

Streaming Pool: reuse, combine and create reactive streams with pleasure

CERN Multimedia

CERN. Geneva

2017-01-01

When connecting together heterogeneous and complex systems, it is not easy to exchange data between components. Streams of data are successfully used in industry in order to overcome this problem, especially in the case of "live" data. Streams are a specialization of the Observer design pattern and they provide asynchronous and non-blocking data flow. The ongoing effort of the ReactiveX initiative is one example that demonstrates how demanding this technology is even for big companies. Bridging the discrepancies of different technologies with common interfaces is already done by the Reactive Streams initiative and, in the JVM world, via reactive-streams-jvm interfaces. Streaming Pool is a framework for providing and discovering reactive streams. Through the mechanism of dependency injection provided by the Spring Framework, Streaming Pool provides a so called Discovery Service. This object can discover and chain streams of data that are technologically agnostic, through the use of Stream IDs. The stream to ...