WorldWideScience

Sample records for chemically reactive ions

  1. 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.

  2. 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

  3. 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).

  4. Production of chemically reactive radioactive ion beams through on-line separation

    International Nuclear Information System (INIS)

    Joinet, A.

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO 2 , Nb, Ti, V,TiO 2 , CeO x , ThO 2 , C, ZrC 4 and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target

  5. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    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 by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  6. Production of chemically reactive radioactive ion beams through on-line separation; Production de faisceaux d'ions radioactifs chimiquement reactifs par separation en ligne

    Energy Technology Data Exchange (ETDEWEB)

    Joinet, A

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO{sub 2}, Nb, Ti, V,TiO{sub 2}, CeO{sub x}, ThO{sub 2}, C, ZrC{sub 4} and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target.

  7. Production of chemically reactive radioactive ion beams through on-line separation; Production de faisceaux d'ions radioactifs chimiquement reactifs par separation en ligne

    Energy Technology Data Exchange (ETDEWEB)

    Joinet, A

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO{sub 2}, Nb, Ti, V,TiO{sub 2}, CeO{sub x}, ThO{sub 2}, C, ZrC{sub 4} and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target.

  8. 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)

  9. 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.

  10. Reactive ion etching of microphotonic structures

    International Nuclear Information System (INIS)

    Du, J.; Glasscock, J.; Vanajek, J.; Savvides, N.

    2004-01-01

    Full text: Fabrication of microphotonic structures such as planar waveguides and other periodic structures based on silicon technology has become increasingly important due to the potential for integration of planar optical devices. We have fabricated various periodic microstructures on silicon wafers using standard optical lithography and reactive ion etching (RIE). For optical applications the surface roughness and the sidewall angle or steepness of microstructures are the most critical factors. In particular, sidewall roughness of the etched waveguide core accounts for most of the optical propagation loss. We show that by varying the main RIE parameters such as gas pressure, RF power and CF 4 /Ar/O 2 gas composition it is possible to produce microstructures with near-vertical sidewalls and very smooth surfaces. In addition to plasma etching conditions, poor edge quality of the mask often causes sidewall roughness. We employed Ni/Cr metal masks in these experiments for deep etching, and used Ar + ion milling instead of wet chemical etching to open the mask. This improves the edge quality of the mask and ultimately results in smooth sidewalls

  11. Surface characterization after subaperture reactive ion beam etching

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Arnold, Thomas; Rauschenbach, Bernd [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Leipzig (Germany)

    2010-07-01

    In usual ion beam etching processes using inert gas (Ar, Xe, Kr..) the material removal is determined by physical sputtering effects on the surface. The admixture of suitable gases (CF{sub 4}+O{sub 2}) into the glow discharge of the ion beam source leads to the generation of reactive particles, which are accelerated towards the substrate where they enhance the sputtering process by formation of volatile chemical reaction products. During the last two decades research in Reactive Ion Beam Etching (RIBE) has been done using a broad beam ion source which allows the treatment of smaller samples (diameter sample < diameter beam). Our goal was to apply a sub-aperture Kaufman-type ion source in combination with an applicative movement of the sample with respect to the source, which enables us to etch areas larger than the typical lateral dimensions of the ion beam. Concerning this matter, the etching behavior in the beam periphery plays a decisive role and has to be investigated. We use interferometry to characterize the final surface topography and XPS measurements to analyze the chemical composition of the samples after RIBE.

  12. 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)

  13. Transport of secondary electrons and reactive species in ion tracks

    Science.gov (United States)

    Surdutovich, Eugene; Solov'yov, Andrey V.

    2015-08-01

    The transport of reactive species brought about by ions traversing tissue-like medium is analysed analytically. Secondary electrons ejected by ions are capable of ionizing other molecules; the transport of these generations of electrons is studied using the random walk approximation until these electrons remain ballistic. Then, the distribution of solvated electrons produced as a result of interaction of low-energy electrons with water molecules is obtained. The radial distribution of energy loss by ions and secondary electrons to the medium yields the initial radial dose distribution, which can be used as initial conditions for the predicted shock waves. The formation, diffusion, and chemical evolution of hydroxyl radicals in liquid water are studied as well. COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy.

  14. Adherent zirconia films by reactive ion implantation

    International Nuclear Information System (INIS)

    Bunker, S.N.; Armini, A.J.

    1993-01-01

    Conventional methods of forming ceramic coatings on metal substrates, such as CVD or plasma spray, typically retain a sharp interface and may have adhesion problems. In order to produce a completely mixed interface for better adhesion, a method using reactive ion implantation was used which can grow a thick stoichiometric film of an oxide ceramic starting from inside the substrate. Zirconium oxide ceramic films have been produced by this technique using a high-energy zirconium ion beam in an oxygen gas ambient. Compositional data are shown based on Auger electron spectroscopy of the film. Tribological properties of the layer were determined from wear and friction measurements using a pin-on-disk test apparatus. The adhesion was measured both by a scratch technique as well as by thermal shock. Results show an extremely adherent ZrO 2 film with good tribological properties

  15. Reactive ion assisted deposition of aluminum oxynitride thin films

    International Nuclear Information System (INIS)

    Hwangbo, C.K.; Lingg, L.J.; Lehan, J.P.; Macleod, H.A.; Suits, F.

    1989-01-01

    Optical properties, stoichiometry, chemical bonding states, and crystal structure of aluminum oxynitride (AlO/sub x/N/sub y/) thin films prepared by reactive ion assisted deposition were investigated. The results show that by controlling the amount of reactive gases the refractive index of aluminum oxynitride films at 550 nm is able to be varied from 1.65 to 1.83 with a very small extinction coefficient. Variations of optical constants and chemical bonding states of aluminum oxynitride films are related to the stoichiometry. From an x-ray photoelectron spectroscopy analysis it is observed that our aluminum oxynitride film is not simply a mixture of aluminum oxide and aluminum nitride but a continuously variable compound. The aluminum oxynitride films are amorphous from an x-ray diffraction analysis. A rugate filter using a step index profile of aluminum oxynitride films was fabricated by nitrogen ion beam bombardment of a growing Al film with backfill oxygen pressure as the sole variation. This filter shows a high resistivity to atmospheric moisture adsorption, suggesting that the packing density of aluminum oxynitride films is close to unity and the energetic ion bombardment densifies the film as well as forming the compound

  16. Rock fracture processes in chemically reactive environments

    Science.gov (United States)

    Eichhubl, P.

    2015-12-01

    Rock fracture is traditionally viewed as a brittle process involving damage nucleation and growth in a zone ahead of a larger fracture, resulting in fracture propagation once a threshold loading stress is exceeded. It is now increasingly recognized that coupled chemical-mechanical processes influence fracture growth in wide range of subsurface conditions that include igneous, metamorphic, and geothermal systems, and diagenetically reactive sedimentary systems with possible applications to hydrocarbon extraction and CO2 sequestration. Fracture processes aided or driven by chemical change can affect the onset of fracture, fracture shape and branching characteristics, and fracture network geometry, thus influencing mechanical strength and flow properties of rock systems. We are investigating two fundamental modes of chemical-mechanical interactions associated with fracture growth: 1. Fracture propagation may be aided by chemical dissolution or hydration reactions at the fracture tip allowing fracture propagation under subcritical stress loading conditions. We are evaluating effects of environmental conditions on critical (fracture toughness KIc) and subcritical (subcritical index) fracture properties using double torsion fracture mechanics tests on shale and sandstone. Depending on rock composition, the presence of reactive aqueous fluids can increase or decrease KIc and/or subcritical index. 2. Fracture may be concurrent with distributed dissolution-precipitation reactions in the hostrock beyond the immediate vicinity of the fracture tip. Reconstructing the fracture opening history recorded in crack-seal fracture cement of deeply buried sandstone we find that fracture length growth and fracture opening can be decoupled, with a phase of initial length growth followed by a phase of dominant fracture opening. This suggests that mechanical crack-tip failure processes, possibly aided by chemical crack-tip weakening, and distributed solution-precipitation creep in the

  17. Dependence of energy per molecule on sputtering yields with reactive gas cluster ions

    International Nuclear Information System (INIS)

    Toyoda, Noriaki; Yamada, Isao

    2010-01-01

    Gas cluster ions show dense energy deposition on a target surface, which result in the enhancement of chemical reactions. In reactive sputtering with gas cluster ions, the energy per atom or molecule plays an important role. In this study, the average cluster size (N, the number of atoms or molecules in a cluster ion) was controlled; thereby the dependences of the energy per molecule on the sputtering yields of carbon by CO 2 cluster ions and that of Si by SF 6 /Ar mixed gas cluster ions were investigated. Large CO 2 cluster ions with energy per molecule of 1 eV showed high reactive sputtering yield of an amorphous carbon film. However, these ions did not cause the formation of large craters on a graphite surface. It is possible to achieve very low damage etching by controlling the energy per molecule of reactive cluster ions. Further, in the case of SF 6 /Ar mixed cluster ions, it was found that reactive sputtering was enhanced when a small amount of SF 6 gas (∼10%) was mixed with Ar. The reactive sputtering yield of Si by one SF 6 molecule linearly increased with the energy per molecule.

  18. Pattern transfer on fused silica samples using sub-aperture reactive ion beam etching

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Arnold, Thomas [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Permoserstrasse 15, D-04318 Leipzig (Germany)

    2012-07-01

    In comparison to sole Ar ion beam sputtering Reactive Ion Beam Etching (RIBE) reveals the main advantage of increasing the selectivity for different kind of materials due to chemical contributions during the material removal. Therefore RIBE is qualified to be an excellent candidate for pattern transfer applications. The goal of the present study is to apply a sub-aperture reactive ion beam for pattern transfer on large fused silica samples. Concerning this matter, the etching behavior in the ion beam periphery plays a decisive role. Using a Kaufman-typed ion source with NF{sub 3} as reactive gas, XPS measurements of the modified surface exposes impurities like Ni, Fe and Cr, which belongs to chemically eroded material of the plasma pot and a layer formation of silicon nitride, handicaps the etching process mainly in the beam periphery where the sputtering contribution decrease. These side effects influence the pattern transfer of trench structures, produced in AZ MIR 701 photoresist by lithography on a 2'' fused silica plate, by changing the selectivity due to modified chemical reactions of the resist layer. Concerning this we investigate a RF-Ion source for sub aperture reactive ion beam applications and finally we examine the pattern transfer on large fused silica plates using NF{sub 3}-sub-aperture RIBE.

  19. 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.

  20. 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.

  1. Pattern transfer on large samples using a sub-aperture reactive ion beam

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Mill, Agnes; Gerlach, Juergen W.; Arnold, Thomas [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Permoserstrasse 15, D-04318 Leipzig (Germany)

    2011-07-01

    In comparison to sole Ar ion beam sputtering Reactive Ion Beam Etching (RIBE) reveals the main advantage of increasing the selectivity for different kind of materials due to chemical contributions during the material removal. Therefore RIBE is qualified to be an excellent candidate for pattern transfer applications. The goal of the present study is to apply a sub-aperture reactive ion beam for pattern transfer on large fused silica samples. Concerning this matter, the etching behavior in the ion beam periphery plays a decisive role. Using CF{sub 4} as reactive gas, XPS measurements of the modified surface exposes impurities like Ni, Fe and Cr, which belongs to chemically eroded material of the plasma pot as well as an accumulation of carbon (up to 40 atomic percent) in the beam periphery, respectively. The substitution of CF{sub 4} by NF{sub 3} as reactive gas reveals a lot of benefits: more stable ion beam conditions in combination with a reduction of the beam size down to a diameter of 5 mm and a reduced amount of the Ni, Fe and Cr contaminations. However, a layer formation of silicon nitride handicaps the chemical contribution of the etching process. These negative side effects influence the transfer of trench structures on quartz by changing the selectivity due to altered chemical reaction of the modified resist layer. Concerning this we investigate the pattern transfer on large fused silica plates using NF{sub 3}-sub-aperture RIBE.

  2. 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

  3. 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

  4. 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...

  5. 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

  6. Deep Reactive Ion Etching for High Aspect Ratio Microelectromechanical Components

    DEFF Research Database (Denmark)

    Jensen, Søren; Yalcinkaya, Arda Deniz; Jacobsen, S.

    2004-01-01

    A deep reactive ion etch (DRIE) process for fabrication of high aspect ratio trenches has been developed. Trenches with aspect ratios exceeding 20 and vertical sidewalls with low roughness have been demonstrated. The process has successfully been used in the fabrication of silicon-on-insulator (SOI...

  7. Control of the ambident reactivity of the nitrite ion

    DEFF Research Database (Denmark)

    Dong, Hai; Rahm, Martin; Thota, Niranjan

    2013-01-01

    of this difference was addressed. The ambident reactivity of the nitrite ion has been found to be the cause of the complex product formation observed, which can be controlled by a neighbouring equatorial ester group. Both N-attack and O-attack occur in the absence of the ester group, whereas O-attack is favoured...

  8. Chemical reactor modeling multiphase reactive flows

    CERN Document Server

    Jakobsen, Hugo A

    2014-01-01

    Chemical Reactor Modeling closes the gap between Chemical Reaction Engineering and Fluid Mechanics.  The second edition consists of two volumes: Volume 1: Fundamentals. Volume 2: Chemical Engineering Applications In volume 1 most of the fundamental theory is presented. A few numerical model simulation application examples are given to elucidate the link between theory and applications. In volume 2 the chemical reactor equipment to be modeled are described. Several engineering models are introduced and discussed. A survey of the frequently used numerical methods, algorithms and schemes is provided. A few practical engineering applications of the modeling tools are presented and discussed. The working principles of several experimental techniques employed in order to get data for model validation are outlined. The monograph is based on lectures regularly taught in the fourth and fifth years graduate courses in transport phenomena and chemical reactor modeling, and in a post graduate course in modern reactor m...

  9. Fragmentation and reactivity of energy-selected ferrocenium ions

    International Nuclear Information System (INIS)

    Mestdagh, H.; Dutuit, O.; Heninger, M.; Thissen, R.; Alcaraz, C.

    2002-01-01

    In this study, results concerning the discussion of state-selected ferrocenium ions (c-C 5 H 5 ) 2 Fe + commonly called Cp 2 Fe + , as well as their reactions with methanol and ethanol are presented. Parent ions Cp 2 Fe + were produced by vacuumultraviolett (VUV) photoionization of neutral ferrocene using synchrotron radiation, and selected in internal energy by threshold photoelectron-photoion coincidences. The apparatus is divided into three differentially pumped regions: the source, the reaction and the detection zones. In source, state-selected parent ions are formed and can be selected in mass by a first quadrupole filter. State-selected ions are then injected in the second zone which is a RF octopole ion guide where reaction product ions are mass analyzed by a second quadrupole filter and detected by microchannelplates. In addition, the long flight time in the octopoles (several hundreds of microseconds) allows studying long-lived metastable ions. Total mass spectra were recorded at different photon energies, in addition to the main CpFe + and Fe + fragments, several minor fragments were detected such as C 10 H 10 + which reflects the formation of a C-C bond between the two Cp ligands. Losses of CH 3 , C 2 H 2 and C-4H 4 also indicate that important structure rearrangements take place before cleavage. The appearance energies of each mass-selected fragment ion were measured by recording fragment ion yields as a function of photon energy. Surprisingly, all fragments were found to have the same energy onset, i.e. 13.2 eV photon energy, except for C 3 H 3 Fe + (m/z 95). For Fe + ions, a sharp increase was observed at 17 eV, above the thermochemical onset of Fe + + 2 Cp. The 13.2 eV appearance energy of Fe + is thus assigned to the formation of Fe - + C 10 H 10 . The reactivity of ferrocenium ion with methanol and ethanol was investigated as a function of photon energy. While no reaction occurs at lower photon energies, several reaction products appear at 13.0 e

  10. Metal ion separations using reactive membranes

    International Nuclear Information System (INIS)

    Way, J.D.

    1993-01-01

    A membrane is a barrier between two phases. If one component of a mixture moves through the membrane faster than another mixture component, a separation can be accomplished. Membranes are used commercially for many applications including gas separations, water purification, particle filtration, and macromolecule separations (Abelson). There are two points to note concerning this definition. First, a membrane is defined based on its function, not the material used to make the membrane. Secondly, a membrane separation is a rate process. The separation is accomplished by a driving force, not by equilibrium between phases. Liquids that are immiscible with the feed and product streams can also be used as membrane materials. Different solutes will have different solubilities and diffusion coefficients in a liquid. The product of the diffusivity and the solubility is known as the permeability coefficient, which is proportional to the solute flux. Differences in permeability coefficient will produce a separation between solutes at constant driving force. Because the diffusion coefficients in liquids are typically orders of magnitude higher than in polymers, a larger flux can be obtained. Further enhancements can be accomplished by adding a nonvolatile complexation agent to the liquid membrane. One can then have either coupled or facilitated transport of metal ions through a liquid membrane. The author describes two implementations of this concept, one involving a liquid membrane supported on a microporous membrane, and the other an emulsion liquid membrane, where separation occurs to internal receiving phases. Applications and costing studies for this technology are reviewed, and a brief summary of some of the problems with liquid membranes is presented

  11. Activation of Reactive MALDI Adduct Ions Enables Differentiation of Dihydroxylated Vitamin D Isomers

    Science.gov (United States)

    Qi, Yulin; Müller, Miriam J.; Volmer, Dietrich A.

    2017-12-01

    Vitamin D compounds are secosteroids, which are best known for their role in bone health. More recent studies have shown that vitamin D metabolites and catabolites such as dihydroxylated species (e.g., 1,25- and 24,25-dihydroxyvitamin D3) play key roles in the pathologies of various diseases. Identification of these isomers by mass spectrometry is challenging and currently relies on liquid chromatography, as the isomers exhibit virtually identical product ion spectra under collision induced dissociation conditions. Here, we developed a simple MALDI-CID method that utilizes ion activation of reactive analyte/matrix adducts to distinguish isomeric dihydroxyvitamin D3 species, without the need for chromatography separation or chemical derivatization techniques. Specifically, reactive 1,5-diaminonaphthalene adducts of dihydroxyvitamin D3 compounds formed during MADI were activated and specific cleavages in the secosteroid's backbone structure were achieved that produced isomer-diagnostic fragment ions. [Figure not available: see fulltext.

  12. Reactivity of the cadmium ion in concentrated phosphoric acid solutions.

    Science.gov (United States)

    De Gyves, J; Gonzales, J; Louis, C; Bessiere, J

    1989-07-01

    The solvation transfer coefficients which characterize the changes of ion reactivity with phosphoric acid concentration have been calculated for cadmium from the constants of the successive chloride complexes, and for silver and diethyldithiophosphate from potentiometric measurements. They evidence the strong desolvation of the cadmium species in concentrated phosphoric acid media, causing a remarkable increase of its reactivity. They allow the results of liquid-liquid extraction, precipitation and flotation reactions to be correctly interpreted and their changes to be foreseen when the reagents are modified.

  13. Triplasmatron sources for broad and reactive ion beams

    International Nuclear Information System (INIS)

    Lejeune, C.; Grandchamp, J.P.; Kessi, O.; Gilles, J.P.

    1986-01-01

    Two alternative discharge structures, which are both convenient for the extraction of broad and reactive ion beams, are described. They have been designed in order to overcome both lifetime and beam contamination problems while preserving a high ionization efficiency and a smooth plasma uniformity. They both use a hot cathode duoplasmatron discharge to inject ionizing electrons into the main ionization chamber, according to the triplasmatron concept. The triplasmatron multipolar ion source (TMIS) uses the magnetic multipolar containment of both electrons and ions, whereas the triplasmatron reflex ion source (TRIS) uses the electrostatic and geometric containment of the ionizing electrons. The behaviour and performance of both structures are reported and discussed with a special emphasis to the operation with either oxygen or fluorocarbon gases. (author)

  14. 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

  15. Chemical and catalytic effects of ion implantation

    International Nuclear Information System (INIS)

    Wolf, G.K.

    1982-01-01

    Energetic particles are used for inducing chemical reactions as well as for modifying the properties of materials with regard to their bulk and surface chemical behavior. The effects are partly caused by radiation damage or phase intermixing, partly by the chemical properties of the individual bombarding particles. In this contribution a survey of relevant applications of these techniques is presented: (1) Chemical reactions of implanted and recoil atoms and their use for syntheses, doping and labeling of compounds. (2) The formation of thin films by decomposing chemical compounds with ion beams. 3) Catalytic effects on substrates treated by sputtering or ion implantation. Recent results with nonmetallic substrates are reviewed. Mainly hydrogenation reactions at a solid/gas interface or redox reactions at an electrified solid/liquid interface are mentioned. The present status and future prospects of these kinds of investigations will be discussed. (author)

  16. Chemical reactivities of some interstellar molecules

    Energy Technology Data Exchange (ETDEWEB)

    Chadha, M S

    1980-01-01

    Work in the area of chemical evolution during the last 25 years has revealed the formation of a large number of biologically important molecules produced from simple starting materials under relatively simple experimental conditions. Much of this work has resulted from studies under atmospheres simulating that of the primitive earth or other planets. During the last decade, progress has also been made in the identification of chemical constituents of interstellar medium. A number of these molecules are the same as those identified in laboratory experiments. Even though the conditions of the laboratory experiments are vastly different from those of the cool, low-density interstellar medium, some of the similarities in composition are too obvious to go unnoticed. The present paper highlights some of the similarities in the composition of prebiotic molecules and those discovered in the interstellar medium. Also the chemical reactions which some of the common molecules e.g., NH3, HCN, H2CO, HC(triple bond)-C-CN etc. can undergo are surveyed.

  17. Freestanding nanostructures via reactive ion beam angled etching

    Directory of Open Access Journals (Sweden)

    Haig A. Atikian

    2017-05-01

    Full Text Available Freestanding nanostructures play an important role in optical and mechanical devices for classical and quantum applications. Here, we use reactive ion beam angled etching to fabricate optical resonators in bulk polycrystalline and single crystal diamond. Reported quality factors are approximately 30 000 and 286 000, respectively. The devices show uniformity across 25 mm samples, a significant improvement over comparable techniques yielding freestanding nanostructures.

  18. 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.

  19. 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.

  20. Modeling of altered layer formation during reactive ion etching of GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Mutzke, A. [Max-Planck-Institute of Plasmaphysics, EURATOM Association, D-17491 Greifswald (Germany); Rai, A., E-mail: Abha.Rai@ipp.mpg.de [Max-Planck-Institute of Plasmaphysics, EURATOM Association, D-17491 Greifswald (Germany); Schneider, R.; Angelin, E.J.; Hippler, R. [Institute of Physics, Ernst-Moritz-Arndt-University Greifswald, Felix-Hausdorff-Str.6, D-17489 Greifswald (Germany)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer Experimental result showing the preferential sputtering of GaAs (150 keV Ar{sup +} and thermal O on GaAs) during reactive ion beam etching (RIBE) has been reported. Black-Right-Pointing-Pointer A model based on binary collisions (SDTrimSP) is presented to simulate RIBE. Black-Right-Pointing-Pointer The model is used to explain the reported experimental data and also the results by Grigonis and co-workers [1]. - Abstract: The binary collision based SDTrimSP model has been used to simulate the reactive ion beam etching (RIBE) of GaAs in the presence of energetic Ar ions and thermal O atoms. It includes the collisional effects, diffusive processes and chemical reactions taking place in the system. The model parameters are fitted using the experimental observations of Grigonis and co-workers [1] and validated with the experimental results obtained during the GaAs ion etching presented in this paper. A detailed analysis is presented to understand the effect of the diffusive processes and the role of O during RIBE of GaAs. It is shown how the presence of damage caused by the energetic Ar coupled with the presence of thermal O opens up chemical reaction channels which eventually leads to the preferential sputtering of Ga observed at the ion etching facility at University of Greifswald.

  1. 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.

  2. Slow Invariant Manifolds in Chemically Reactive Systems

    Science.gov (United States)

    Paolucci, Samuel; Powers, Joseph M.

    2006-11-01

    The scientific design of practical gas phase combustion devices has come to rely on the use of mathematical models which include detailed chemical kinetics. Such models intrinsically admit a wide range of scales which renders their accurate numerical approximation difficult. Over the past decade, rational strategies, such as Intrinsic Low Dimensional Manifolds (ILDM) or Computational Singular Perturbations (CSP), for equilibrating fast time scale events have been successfully developed, though their computation can be challenging and their accuracy in most cases uncertain. Both are approximations to the preferable slow invariant manifold which best describes how the system evolves in the long time limit. Strategies for computing the slow invariant manifold are examined, and results are presented for practical combustion systems.

  3. 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)

  4. Chemical sputtering of graphite by H+ ions

    International Nuclear Information System (INIS)

    Busharov, N.P.; Gorbatov, E.A.; Gusev, V.M.; Guseva, M.I.; Martynenko, Y.V.

    1976-01-01

    In a study of the sputtering coefficient S for the sputtering of graphite by 10-keV H + ions as a function of the graphite temperature during the bombardment, it is found that at T> or =750degreeC the coefficient S is independent of the target temperature and has an anomalously high value, S=0.085 atom/ion. The high rate of sputtering of graphite by atomic hydrogen ions is shown to be due to chemical sputtering of the graphite, resulting primarily in the formation of CH 4 molecules. At T=1100degreeC, S falls off by a factor of about 3. A model for the chemical sputtering of graphite is proposed

  5. Chemical atomization of graphite by H+ ions

    International Nuclear Information System (INIS)

    Busharov, I.P.; Gorbatov, E.A.; Gusev, V.M.; Guseva, M.I.; Martynenko, Yu.V.

    A simple model of the mechanism of chemical atomization is given, on whose basis a decrease in chemical atomization is qualitatively predicted for high temperatures. Mass spectrometric investigations of the atomization products cited, which found CH 4 and CH 3 molecules during the irradiation of graphite and H + ions thereby confirmed the presence of chemical atomization. A relationship of S and temperature of graphite T during irradiation was obtained which showed a decrease in the coefficient of atomization of a high temperature. (U.S.)

  6. 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...

  7. Ion reactivity of calcium-deficient hydroxyapatite in standard cell culture media.

    Science.gov (United States)

    Gustavsson, J; Ginebra, M P; Engel, E; Planell, J

    2011-12-01

    Solution-mediated surface reactions occur for most calcium phosphate-based biomaterials and may influence cellular response. A reasonable extrapolation of such processes observed in vitro to in vivo performance requires a deep understanding of the underlying mechanisms. We therefore systematically investigated the nature of ion reactivity of calcium-deficient hydroxyapatite (CDHA) by exposing it for different periods of time to standard cell culture media of different chemical composition (DMEM and McCoy medium, with and without osteogenic supplements and serum proteins). Kinetic ion interaction studies of principal extracellular ions revealed non-linear sorption of Ca²⁺ (∼50% sorption) and K⁺ (∼8%) as well as acidification of all media during initial contact with CDHA (48h). Interestingly, inorganic phosphorus (P(i)) was sorbed from McCoy medium (∼50%) or when using osteogenic media containing β-glycerophosphate, but not from DMEM medium. Non-linear sorption data could be perfectly described by pseudo-first-order and pseudo-second-order sorption models. At longer contact time (21 days), and with frequent renewal of culture medium, sorption of Ca²⁺ remained constant throughout the experiment, while sorption of P(i) gradually decreased in McCoy medium. In great contrast, CDHA began to release P(i) slowly with time when using DMEM medium. Infrared spectra showed that CDHA exposed to culture media had a carbonated surface chemistry, suggesting that carbonate plays a key role in the ion reactivity of CDHA. Our data show that different compositions of the aqueous environment may provoke opposite ion reactivity of CDHA, and this must be carefully considered when evaluating the osteoinductive potential of the material. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  8. Heavy ion measurement by chemical detectors

    International Nuclear Information System (INIS)

    Huebner, K.; Erzgraeber, G.; Eichhorn, K.

    1979-02-01

    In testing the applicability of the threshold system polyvinyl alcohol/methyl orange/chloral hydrate/sodium tetraborate to the quantitative detection of single particles, the chemical detector was irradiated with 4 He, 12 C, 18 O, 22 He ions of different LET. Detectors with 4 different borax concentrations (chloral hydrate concentration kept constant) have been irradiated. The dose causing the colour change increased linearly with the borax concentration. For equal borax concentrations this dose increases with increasing LET due to the decreasing G value of the HCl. The fluence ranges measurable with the various detector compositions are given. 4 He and 18 O ion ranges have been determined. The measured depth dose curves have been corrected because the dose is LET-dependent. The experimentally determined ranges are in good agreement with values calculated for the detector material

  9. Periodic arrays of deep nanopores made in silicon with reactive ion etching and deep UV lithography

    International Nuclear Information System (INIS)

    Woldering, Leon A; Tjerkstra, R Willem; Vos, Willem L; Jansen, Henri V; Setija, Irwan D

    2008-01-01

    We report on the fabrication of periodic arrays of deep nanopores with high aspect ratios in crystalline silicon. The radii and pitches of the pores were defined in a chromium mask by means of deep UV scan and step technology. The pores were etched with a reactive ion etching process with SF 6 , optimized for the formation of deep nanopores. We have realized structures with pitches between 440 and 750 nm, pore diameters between 310 and 515 nm, and depth to diameter aspect ratios up to 16. To the best of our knowledge, this is the highest aspect ratio ever reported for arrays of nanopores in silicon made with a reactive ion etching process. Our experimental results show that the etching rate of the nanopores is aspect-ratio-dependent, and is mostly influenced by the angular distribution of the etching ions. Furthermore we show both experimentally and theoretically that, for sub-micrometer structures, reducing the sidewall erosion is the best way to maximize the aspect ratio of the pores. Our structures have potential applications in chemical sensors, in the control of liquid wetting of surfaces, and as capacitors in high-frequency electronics. We demonstrate by means of optical reflectivity that our high-quality structures are very well suited as photonic crystals. Since the process studied is compatible with existing CMOS semiconductor fabrication, it allows for the incorporation of the etched arrays in silicon chips

  10. The reactivity of ion-implanted SiC

    International Nuclear Information System (INIS)

    McHargue, C.J.; Lewis, M.B.; Williams, J.M.; Appleton, B.R.

    1985-01-01

    Implantation of chromium into single crystal or polycrystalline α-SiC produces a surface amorphous layer for displacement damage greater than about 0.2 displacements per atom at room temperature. The enhanced chemical reactivity of such specimens was studied by two methods: chemical etching rate and oxidation rate. The chemical etching rates in a saturated solution of 50% K 3 Fe(CN) 6 plus 50% KOH were measured. The etching rate for the amorphous layer was 2.4-3.7 times that of the polycrystalline samples and 3.0-4.1 times that of the single-crystal samples. Polycrystalline specimens were exposed to flowing oxygen for 1 h at 1300 0 C. Rutherford backscattering and the nuclear reaction 16 O(d,p) 17 O* were used to determine the amount of oxygen on the surface. The amount of oxygen (and the thickness of oxide) over the amorphous region was 1.67 times that over the crystalline region. The relative thicknesses of the oxide on the amorphous and crystalline regions were confirmed by measuring the sputtering time required to remove the oxygen signal in an Auger spectrometer. (Auth.)

  11. Polymer degradation in reactive ion etching and its possible application to all dry processes

    International Nuclear Information System (INIS)

    Hiraoka, H.; Welsh, L.W. Jr.

    1981-01-01

    Dry etching processes involving CF 4 -plasma and reactive ion etching become increasingly important for microcircuit fabrication techniques. In these techniques polymer degradation and etch resistance against reactive species like F atoms and CF 3 + ions are the key factors in the processes. It is well-known that classical electron beam resists like poly(methyl methacrylate) and poly(1-butene sulfone) are not suitable for dry etching processes because they degrade rapidly under these etching conditions. In order to find a correlation of etching rate and polymer structures the thickness loss of polymer films have been measured for a variety of polymer films in reactive ion etching conditions, where CF 3 + ions are the major reactive species with an accelerating potential of 500 volts. Because of its high CF 4 -plasma and reactive ion etch resistance, and because of its high electron beam sensitivity, poly(methacrylonitrile) provides a positive working electron beam resist uniquely suited for all dry processes. (author)

  12. A Reactive-Ion Etch for Patterning Piezoelectric Thin Film

    Science.gov (United States)

    Yang, Eui-Hyeok; Wild, Larry

    2003-01-01

    Reactive-ion etching (RIE) under conditions described below has been found to be a suitable means for patterning piezoelectric thin films made from such materials as PbZr(1-x)Ti(x)O3 or Ba(x)Sr(1.x)TiO3. In the original application for which this particular RIE process was developed, PbZr(1-x)Ti(x)O3 films 0.5 microns thick are to be sandwiched between Pt electrode layers 0.1 microns thick and Ir electrode layers 0.1 microns thick to form piezoelectric capacitor structures. Such structures are typical of piezoelectric actuators in advanced microelectromechanical systems now under development or planned to be developed in the near future. RIE of PbZr(1-x)Ti(x)O3 is usually considered to involve two major subprocesses: an ion-assisted- etching reaction, and a sputtering subprocess that removes reactive byproducts. RIE is favored over other etching techniques because it offers a potential for a high degree of anisotropy, high-resolution pattern definition, and good process control. However, conventional RIE is not ideal for patterning PbZr(1-x)Ti(x)O3 films at a thickness as great as that in the original intended application. In order to realize the potential benefits mentioned above, it is necessary to optimize process conditions . in particular, the composition of the etching gas and the values of such other process parameters as radio-frequency power, gas pressure, gas-flow rate, and duration of the process. Guidelines for determining optimum conditions can be obtained from experimental determination of etch rates as functions of these parameters. Etch-gas mixtures of BCl3 and Cl2, some also including Ar, have been found to offer a high degree of selectivity as needed for patterning of PbZr(1-x)Ti(x)O3 films on top of Ir electrode layers in thin-film capacitor structures. The selectivity is characterized by a ratio of approx.10:1 (rate of etching PbZr(1-x)Ti(x)O3 divided by rate of etching Ir and IrO(x)). At the time of reporting the information for this article

  13. 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.

  14. 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

  15. Etching radical controlled gas chopped deep reactive ion etching

    Science.gov (United States)

    Olynick, Deidre; Rangelow, Ivo; Chao, Weilun

    2013-10-01

    A method for silicon micromachining techniques based on high aspect ratio reactive ion etching with gas chopping has been developed capable of producing essentially scallop-free, smooth, sidewall surfaces. The method uses precisely controlled, alternated (or chopped) gas flow of the etching and deposition gas precursors to produce a controllable sidewall passivation capable of high anisotropy. The dynamic control of sidewall passivation is achieved by carefully controlling fluorine radical presence with moderator gasses, such as CH.sub.4 and controlling the passivation rate and stoichiometry using a CF.sub.2 source. In this manner, sidewall polymer deposition thicknesses are very well controlled, reducing sidewall ripples to very small levels. By combining inductively coupled plasmas with controlled fluorocarbon chemistry, good control of vertical structures with very low sidewall roughness may be produced. Results show silicon features with an aspect ratio of 20:1 for 10 nm features with applicability to nano-applications in the sub-50 nm regime. By comparison, previous traditional gas chopping techniques have produced rippled or scalloped sidewalls in a range of 50 to 100 nm roughness.

  16. 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.

  17. Chemical Shuttle Additives in Lithium Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, Mary

    2013-03-31

    than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.

  18. Chemical equilibration in relativistic heavy ion collisions

    International Nuclear Information System (INIS)

    Brown, Gerald E.; Lee, Chang-Hwan; Rho, Mannque

    2005-01-01

    In the hadronic sector of relativistic heavy ion physics, the ρ<-2π reaction is the strongest one, strong enough to equilibrate the ρ with the pions throughout the region from chemical freezeout to thermal freezeout when free-particle interactions (with no medium-dependent effects) are employed. Above the chiral restoration temperature, only ρ's and π's are present, in that the chirally restored A1 is equivalent to the ρ and the mesons have an SU(4) symmetry, with no dependence on isospin and negligible dependence on spin. In the same sense the σ and π are 'equivalent' scalars. Thus the chirally restored ρ<-2π exhaust the interspecies transitions. We evaluate this reaction at Tc and find it to be much larger than below Tc, certainly strong enough to equilibrate the chirally restored mesons just above Tc. When emitted just below Tc the mesons remain in the Tc+ε freezeout distribution, at least in the chiral limit because of the Harada-Yamawaki 'vector manifestation' that requires that mesonic coupling constants go to zero (in the chiral limit) as T goes to Tc from below. Our estimates in the chiral limit give deviations in some particle ratios from the standard scenario (of equilibrium in the hadronic sector just below Tc) of about double those indicated experimentally. This may be due to the neglect of explicit chiral symmetry breaking in our estimates. We also show that the instanton molecules present above Tc are the giant multipole vibrations found by Asakawa, Hatsuda and Nakahara and of Wetzorke et al. in lattice gauge calculations. Thus, the matter formed by RHIC can equivalently be called: chirally restored mesons, instanton molecules, or giant collective vibrations. It is a strongly interacting liquid

  19. 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.

  20. Attenuation of Chemical Reactivity of Shale Matrixes following Scale Precipitation

    Science.gov (United States)

    Li, Q.; Jew, A. D.; Kohli, A. H.; Alalli, G.; Kiss, A. M.; Kovscek, A. R.; Zoback, M. D.; Brown, G. E.; Maher, K.; Bargar, J.

    2017-12-01

    Introduction of fracture fluids into shales initiates a myriad of fluid-rock reactions that can strongly influence migration of fluid and hydrocarbon through shale/fracture interfaces. Due to the extremely low permeability of shale matrixes, studies on chemical reactivity of shales have mostly focused on shale surfaces. Shale-fluid interactions inside within shale matrixes have not been examined, yet the matrix is the primary conduit through which hydrocarbons and potential contaminants are transmitted. To characterize changes in matrix mineralogy, porosity, diffusivity, and permeability during hydraulic stimulation, we reacted Marcellus (high clay and low carbonate) and Eagle Ford (low clay and high carbonate) shale cores with fracture fluids for 3 weeks at elevated pressure and temperature (80 oC, and 77 bars). In the carbonate-poor Marcellus system, fluid pH increased from 2 to 4, and secondary Fe(OH)3 precipitates were observed in the fluid. Sulfur X-ray fluorescence maps show that fluids had saturated and reacted with the entire 1-cm-diameter core. In the carbonate-rich Eagle Ford system, pH increased from 2 to 6 due to calcite dissolution. When additional Ba2+ and SO42- were present (log10(Q/K)=1.3), extensive barite precipitation was observed in the matrix of the Eagle Ford core (and on the surface). Barite precipitation was also observed on the surface of the Marcellus core, although to a lesser extent. In the Marcellus system, the presence of barite scale attenuated diffusivity in the matrix, as demonstrated by sharply reduced Fe leaching and much less sulfide oxidation. Systematic studies in homogeneous solution show that barite scale precipitation rates are highly sensitive to pH, salinity, and the presence of organic compounds. These findings imply that chemical reactions are not confined to shale/fluid interfaces but can penetrate into shale matrices, and that barite scale formation can clog diffusion pathways for both fluid and hydrocarbon.

  1. 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.

  2. 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.

  3. Reactive Chemical Vapor Deposition Method as New Approach for Obtaining Electroluminescent Thin Film Materials

    Directory of Open Access Journals (Sweden)

    Valentina V. Utochnikova

    2012-01-01

    Full Text Available The new reactive chemical vapor deposition (RCVD method has been proposed for thin film deposition of luminescent nonvolatile lanthanide aromatic carboxylates. This method is based on metathesis reaction between the vapors of volatile lanthanide dipivaloylmethanate (Ln(dpm3 and carboxylic acid (HCarb orH2Carb′ and was successfully used in case of HCarb. Advantages of the method were demonstrated on example of terbium benzoate (Tb(bz3 and o-phenoxybenzoate thin films, and Tb(bz3 thin films were successfully examined in the OLED with the following structure glass/ITO/PEDOT:PSS/TPD/Tb(bz3/Ca/Al. Electroluminescence spectra of Tb(bz3 showed only typical luminescent bands, originated from transitions of the terbium ion. Method peculiarities for deposition of compounds of dibasic acids H2Carb′ are established on example of terbium and europium terephtalates and europium 2,6-naphtalenedicarboxylate.

  4. Encoding of Fundamental Chemical Entities of Organic Reactivity Interest using chemical ontology and XML.

    Science.gov (United States)

    Durairaj, Vijayasarathi; Punnaivanam, Sankar

    2015-09-01

    Fundamental chemical entities are identified in the context of organic reactivity and classified as appropriate concept classes namely ElectronEntity, AtomEntity, AtomGroupEntity, FunctionalGroupEntity and MolecularEntity. The entity classes and their subclasses are organized into a chemical ontology named "ChemEnt" for the purpose of assertion, restriction and modification of properties through entity relations. Individual instances of entity classes are defined and encoded as a library of chemical entities in XML. The instances of entity classes are distinguished with a unique notation and identification values in order to map them with the ontology definitions. A model GUI named Entity Table is created to view graphical representations of all the entity instances. The detection of chemical entities in chemical structures is achieved through suitable algorithms. The possibility of asserting properties to the entities at different levels and the mechanism of property flow within the hierarchical entity levels is outlined. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Chemical uranium enrichment with ion exchanger

    International Nuclear Information System (INIS)

    Takeda, Kunihiko; Onitsuka, Hatsuki; Obanawa, Heiichiro

    1991-01-01

    The uranium enrichment by using ion-exchange has been studied and developed since 1972. The ion-exchange rate has been improved approx. 3000 times and the electron exchange reaction, which occurs with ion-exchange reaction, was also accelerated with catalyst. Flow disturbance in a ion-exchange column has been fully studied and the value of turbulence has been reduced to 150μm. These results allowed us to design a very fine separation column, in which about 10000 stages can be obtained even when the column is more than 1 m in diameter. In the course of the development, a self-regenerating reaction between the redox agents was discovered and incorporated into the process, and has resulted in a reduction of 70 % in the separation energy requirement. (author)

  6. 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

  7. Reactive Landing of Dendrimer Ions onto Activated Self-assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Qichi; Laskin, Julia

    2014-02-06

    The reactivity of gaseous, amine-terminated polyamidoamine (PAMAM) dendrimer ions with activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester groups (NHS-SAM) is examined using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS). The reaction extent is determined from depletion of the infrared band at 1753 cm-1, corresponding to the stretching vibration of the NHS carbonyl groups following ion deposition. For reaction yields below 10%, NHS band depletion follows a linear dependence on the ion dose. By comparing the kinetics plots obtained for 1,12-dodecanediamine and different generations of dendrimer ions (G0–G3) containing 4, 8, 16, and 32 terminal amino group, we demonstrate that the relative reaction efficiency increases linearly with the number of NH2 groups in the molecule. This finding is rationalized assuming the formation of multiple amide bonds upon collision of higher-generation dendrimers with NHS-SAM. Furthermore, by comparing the NHS band depletion following deposition of [M+4H]4+ ions of the G2 dendrimer at 30, 80, and 120 eV, we demonstrate that the ion’s kinetic energy has no measurable effect on reaction efficiency. Similarly, the ion’s charge state only has a minor effect on the reactive landing efficiency of dendrimer ions. Our results indicate that reactive landing is an efficient approach for highly selective covalent immobilization of complex multifunctional molecules onto organic surfaces terminated with labile functional groups.

  8. 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

  9. Fabrication of submicron structures in nanoparticle/polymer composite by holographic lithography and reactive ion etching

    Science.gov (United States)

    Zhang, A. Ping; He, Sailing; Kim, Kyoung Tae; Yoon, Yong-Kyu; Burzynski, Ryszard; Samoc, Marek; Prasad, Paras N.

    2008-11-01

    We report on the fabrication of nanoparticle/polymer submicron structures by combining holographic lithography and reactive ion etching. Silica nanoparticles are uniformly dispersed in a (SU8) polymer matrix at a high concentration, and in situ polymerization (cross-linking) is used to form a nanoparticle/polymer composite. Another photosensitive SU8 layer cast upon the nanoparticle/SU8 composite layer is structured through holographic lithography, whose pattern is finally transferred to the nanoparticle/SU8 layer by the reactive ion etching process. Honeycomb structures in a submicron scale are experimentally realized in the nanoparticle/SU8 composite.

  10. Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

    Science.gov (United States)

    Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

    2017-12-01

    With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

  11. 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

  12. Chemical reactivity of the compressed noble gas atoms and their ...

    Indian Academy of Sciences (India)

    Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study ...

  13. Effects of anodic potential and chloride ion on overall reactivity in electrochemical reactors designed for solar-powered wastewater treatment.

    Science.gov (United States)

    Cho, Kangwoo; Qu, Yan; Kwon, Daejung; Zhang, Hao; Cid, Clément A; Aryanfar, Asghar; Hoffmann, Michael R

    2014-02-18

    We have investigated electrochemical treatment of real domestic wastewater coupled with simultaneous production of molecular H2 as useful byproduct. The electrolysis cells employ multilayer semiconductor anodes with electroactive bismuth-doped TiO2 functionalities and stainless steel cathodes. DC-powered laboratory-scale electrolysis experiments were performed under static anodic potentials (+2.2 or +3.0 V NHE) using domestic wastewater samples, with added chloride ion in variable concentrations. Greater than 95% reductions in chemical oxygen demand (COD) and ammonium ion were achieved within 6 h. In addition, we experimentally determined a decreasing overall reactivity of reactive chlorine species toward COD with an increasing chloride ion concentration under chlorine radicals (Cl·, Cl2(-)·) generation at +3.0 V NHE. The current efficiency for COD removal was 12% with the lowest specific energy consumption of 96 kWh kgCOD(-1) at the cell voltage of near 4 V in 50 mM chloride. The current efficiency and energy efficiency for H2 generation were calculated to range from 34 to 84% and 14 to 26%, respectively. The hydrogen comprised 35 to 60% by volume of evolved gases. The efficacy of our electrolysis cell was further demonstrated by a 20 L prototype reactor totally powered by a photovoltaic (PV) panel, which was shown to eliminate COD and total coliform bacteria in less than 4 h of treatment.

  14. Reactive ion etching of polymer materials for an energy harvesting device

    DEFF Research Database (Denmark)

    Wang, Fei; Bertelsen, Christian Vinther; Skands, Gustav

    2012-01-01

    In this paper, we have demonstrated deep reactive ion etching (RIE) of two MEMS compatible polymer materials CYTOP and TOPAS, which may be useful for energy harvesting devices. The CYTOP polymer was patterned and used as the electret for the following corona charging while the TOPAS polymer...

  15. 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.

  16. Models for risk assessment of reactive chemicals in aquatic toxicology

    NARCIS (Netherlands)

    Freidig, Andreas Peter

    2000-01-01

    A quantitative structure property relationship (QSPR) for a,b-unsaturated carboxylates (mainly acrylates and methacrylates) was established in chapter 2. Chemical reaction rate constants were measured for 12 different chemicals with three different nucleophiles, namely H 2 O, OH - and glutathione

  17. 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.

  18. Ion exchange nonwoven fabric chemical filter. 2

    International Nuclear Information System (INIS)

    Sekiguchi, Hideaki

    2000-01-01

    This report outlined the characteristics of EPIX filter and its complex with activated carbon to eliminate organic compounds from solvent. Elimination performance of this filter was determined using an ion chromatographic analyzer. EPIX filter showed high performance to eliminate trace amount of ionic compounds. The rate of elimination was both 99% or more for NH 3 and SO 2 in an early phase of filtration. Release of dust as well as impurities was significantly reduced by the use of EPIX filter. Gases once adsorbed on the filter were not released even at an elevated temperature of atmosphere. Combined use of non-woven fabrics was possible. For EPIX filter, there are three kinds; strong acid cation exchange filter and strong/weak basic anion filters. The weak basic anion filter has been applied to the conventional apparatus in wafer makers because the filter was very effective for selective boron trapping. When polyethyleneterephthalate was used as the base polymer, radical groups produced on the polymer were co-polymerized with monomer substances. The lifetime of filter was estimated on a base of gas concentration and wind velocity to determine the time to replace with a new one. Furthermore, the loss of pressure became less than a half when EPIX filter was used. (M.N.)

  19. 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...

  20. Use of reactive gases with broad-beam radio frequency ion sources for industrial applications

    International Nuclear Information System (INIS)

    Schneider, St.; Jolly, T.W.; Kohlstedt, H.; Waser, R.

    2004-01-01

    Broad-beam ion sources are used for a number of important industrial etching and deposition applications, and the use of inductively coupled plasmas has greatly increased the feasibility of using beams of reactive gases, especially of chlorine and oxygen, but also of CO, CO 2 , CF 4 , CHF 3 , SF 6 , etc. In order to gain more understanding of the factors that affect the composition of beams of these gases, we have used a Hiden energy-dispersive quadrupole mass spectrometer to analyze the flux of ions and energetic particles produced by an Oxford Instruments 15 cm rf ion source. For all of the above gases, we have analyzed the effects of changing the operating conditions on the composition of the ion beam, and the fractional production of multiply charged ions; on the plasma potential (and the consequential divergence of the ion beam) and on the spread in energy of the ion beam. We discuss how these factors influence the correct use of the ion source in etching applications with these gases. It is important that the design of the ion source should be optimized for the process gases that are used. The source was originally optimized for use on argon. We discuss the effect of the design on the source's performance with the different gases, and we consider whether design changes would be appropriate for optimum performance on different gases

  1. 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.

  2. 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.

  3. 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.

  4. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Hu, Qichi

    2017-03-13

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS+2H]2+, and two charge states of ubiquitin, [U+5H]5+ and [U+13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs

  5. Films deposited from reactive sputtering of aluminum acetylacetonate under low energy ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Battaglin, Felipe Augusto Darriba; Prado, Eduardo Silva; Cruz, Nilson Cristino da; Rangel, Elidiane Cipriano, E-mail: elidiane@sorocaba.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Sorocaba, SP (Brazil). Lab. de Plasmas Tecnologicos; Caseli, Luciano [Universidade Federal de Sao Paulo (UNIFESP), Diadema, SP (Brazil). Instituto de Ciencias Ambientais, Quimicas e Farmaceuticas; Silva, Tiago Fiorini da; Tabacniks, Manfredo Harri [Universidade de Sao Paulo (USP), SP (Brazil). Instituto de Fisica

    2017-07-15

    Films were deposited from aluminum acetylacetonate (Al(acac)3 ) using a methodology involving reactive sputtering and low energy ion bombardment. The plasma was generated by the application of radiofrequency power to the powder containing electrode and simultaneously, negative pulses were supplied to the electrode where the substrates were attached. It was investigated the effect of the duty cycle of the pulses (Δ) on the properties of the coatings. Association of ion bombardment to the deposition process increased film thickness, structure reticulation and organic content. Ions from the deposition environment were implanted at the film-air interface or underneath it. Morphology and topography were altered depending on Δ. Considering the enhancement of Δ, it affected the flux of ions reaching the depositing interface and then the deposition rate, H content, crosslinking degree and surface microstructure. Alumina groups were detected in the infrared spectra, whereas the precipitation of amorphous alumina was confirmed by X-ray diffraction. (author)

  6. 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.

  7. Reactive formulations for a neutralization of toxic industrial chemicals

    Science.gov (United States)

    Tucker, Mark D [Albuqueruqe, NM; Betty, Rita G [Rio Rancho, NM

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  8. Chemical and Photochemical Reactivity in Microemulsions and Waterless Microemulsions.

    Science.gov (United States)

    1988-02-10

    virtually the same as that found in the alcohol rich microemulsion A. This value is also close to that found in pure butanol (= 5.0 - table I). It would...formamide or alcohol rich). RESEARCH PATTERN -Supplementing the physical chemical study of the microemulsion medium involving ionic surfactants with density...SAMII (1/02/1988) Ii&N 3 Part II - OXYDATIONS BY HYDROPEROXIDES IN MICROEMULSIONS E. OLIVEROS and M.T. MAURETTE During the past six months, the financial

  9. 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.

  10. Tuning silver ion release properties in reactively sputtered Ag/TiOx nanocomposites

    Science.gov (United States)

    Xiong, J.; Ghori, M. Z.; Henkel, B.; Strunskus, T.; Schürmann, U.; Deng, M.; Kienle, L.; Faupel, F.

    2017-07-01

    Silver/titania nanocomposites with strong bactericidal effects and good biocompatibility/environmental safety show a high potential for antibacterial applications. Tailoring the silver ion release is thus highly promising to optimize the antibacterial properties of such coatings and to preserve biocompatibility. Reactive sputtering is a fast and versatile method for the preparation of such Ag/TiOx nanocomposites coatings. The present work is concerned with the influence of sputter parameters on the surface morphology and silver ion release properties of reactively sputtered Ag/TiOx nanocomposites coatings showing a silver nanoparticle size distribution in the range from 1 to 20 nm. It is shown that the silver ion release rate strongly depends on the total pressure: the coatings prepared at lower pressure present a lower but long-lasting release behavior. The much denser structure produced under these conditions reduces the transport of water molecules into the coating. In addition, the influence of microstructure and thickness of titanium oxide barriers on the silver ion release were investigated intensively. Moreover, for the coatings prepared at high total pressure, it was demonstrated that stable and long-lasting silver release can be achieved by depositing a barrier with a high rate. Nanocomposites produced under these conditions show well controllable silver ion release properties for applications as antibacterial coatings.

  11. 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.

  12. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. A novel non-sequential hydrogen-pulsed deep reactive ion etching of silicon

    International Nuclear Information System (INIS)

    Gharooni, M; Mohajerzadeh, A; Sandoughsaz, A; Khanof, S; Mohajerzadeh, S; Asl-Soleimani, E

    2013-01-01

    A non-sequential pulsed-mode deep reactive ion etching of silicon is reported that employs continuous etching and passivation based on SF 6 and H 2 gases. The passivation layer, as an important step for deep vertical etching of silicon, is feasible by hydrogen pulses in proper time-slots. By adjusting the etching parameters such as plasma power, H 2 and SF 6 flows and hydrogen pulse timing, the process can be controlled for minimum underetch and high etch-rate at the same time. High-aspect-ratio features can be realized with low-density plasma power and by controlling the reaction chemistry. The so-called reactive ion etching lag has been minimized by operating the reactor at higher pressures. X-ray photoelectron spectroscopy and scanning electron microscopy have been used to study the formation of the passivation layer and the passivation mechanism. (paper)

  14. In-Situ Ion Source Cleaning: Review of Chemical Mechanisms and Evaluation Data at Production Fabs

    International Nuclear Information System (INIS)

    Kaim, R.; Bishop, S.; Byl, O.; Eldridge, D.; Marganski, P.; Mayer, J.; Sweeney, J.; Yedave, S.; Fuchs, D.; Spreitzer, S.; Vogel, J.; Dunn, J.; Lundquist, P.; Rolland, J.; Romig, T.; Newman, D.; Mitchell, M.; Ditzler, K.

    2008-01-01

    Since the concept of chemical in-situ ion implanter cleaning was introduced at IIT2006 [1], evaluations of the XeF 2 cleaning technology have taken place or are ongoing at more than 40 production fabs worldwide. Testing has been focused on assessing effects of cleaning in the source arc chamber and extraction regions. In this paper we describe use of the cleaning technology in a production environment and summarize evaluation data showing advantages of the technology for improving ion source life, reducing glitching, improving beam auto-tuning and avoiding species cross-contamination. More details of the evaluations are given in several separate papers submitted to this Conference. We have supplemented the fab production data with laboratory experiments designed to investigate the reactivity of XeF 2 and fundamental aspects of the source deposition and cleaning processes. These experiments are summarized here, and more details can be found in separate papers submitted to this Conference

  15. 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.

  16. 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.

  17. An experimental study of steam explosions involving chemically reactive metal

    International Nuclear Information System (INIS)

    Cho, D.H.; Armstrong, D.R.; Gunther, W.H.; Basu, S.

    1997-01-01

    An experimental study of molten zirconium-water explosions was conducted. A 1-kg mass of zirconium melt was dropped into a column of water. Explosions took place only when an external trigger was used. In the triggered tests, the extent of oxidation of the zirconium melt was very extensive. However, the explosion energetics estimated were found to be very small compared to the potential chemical energy available from the oxidation reaction. Zirconium is of particular interest, since it is a component of the core materials of the current nuclear power reactors. This paper describes the test apparatus and summarizes the results of four tests conducted using pure zirconium melt

  18. Cathode and ion-luminescence of Eu:ZnO thin films prepared by reactive magnetron sputtering and plasma decomposition of non-volatile precursors

    Energy Technology Data Exchange (ETDEWEB)

    Gil-Rostra, Jorge [Instituto de Ciencia de Materiales de Sevilla, CSIC, Univ. Sevilla, C/Américo Vespucio 49, E-41092 Sevilla (Spain); Ferrer, Francisco J. [Centro Nacional de Aceleradores, CSIC, Univ. Sevilla, Av. Thomas A. Edison 7, E-41092 Sevilla (Spain); Martín, Inocencio R. [Departamento de Física Fundamental y Experimental, Electrónica y Sistemas, U. La Laguna, C/Astrofísico Francisco Sánchez s/n, E-38206 La Laguna, Santa Cruz de Tenerife (Spain); González-Elipe, Agustín R.; Yubero, Francisco [Instituto de Ciencia de Materiales de Sevilla, CSIC, Univ. Sevilla, C/Américo Vespucio 49, E-41092 Sevilla (Spain)

    2016-10-15

    This paper reports the luminescent behavior of Eu:ZnO thin films prepared by an one-step procedure that combines reactive magnetron sputtering deposition of ZnO with the plasma activated decomposition of a non-volatile acetylacetonate precursor of Eu sublimated in an effusion cell. Chemical composition and microstructure of the Eu:ZnO thin films have been characterized by several methods and their photo-, cathode- and ion-luminescent properties studied as a function of Eu concentration. The high transparency and well controlled optical properties of the films have demonstrated to be ideal for the development of cathode- and ion- luminescence sensors.

  19. 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.

  20. Mask-free surface structuring of micro- and nanocrystalline diamond films by reactive ion plasma etching

    Czech Academy of Sciences Publication Activity Database

    Domonkos, Mária; Ižák, Tibor; Babchenko, Oleg; Varga, Marián; Hruška, Karel; Kromka, Alexander

    2014-01-01

    Roč. 6, č. 7 (2014), s. 780-784 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0910; GA ČR GAP108/12/0996; GA MPO FR-TI2/736 Institutional support: RVO:68378271 Keywords : micro- and nanocrystalline diamond * capacitively coupled plasma * reactive ion etching * nanostructuring * scanning electron microscopy Subject RIV: BM - Solid Matter Physics ; Magnetism

  1. Ion-beam nanopatterning: experimental results with chemically-assisted beam

    Science.gov (United States)

    Pochon, Sebastien C. R.

    2018-03-01

    The need for forming gratings (for example used in VR headsets) in materials such as SiO2 has seen a recent surge in the use of Ion beam etching techniques. However, when using an argon-only beam, the selectivity is limited as it is a physical process. Typically, gases such as CHF3, SF6, O2 and Cl2 can be added to argon in order to increase selectivity; depending on where the gas is injected, the process is known as Reactive Ion Beam Etching (RIBE) or Chemically Assisted Ion Beam Etching (CAIBE). The substrate holder can rotate in order to provide an axisymmetric etch rate profile. It can also be tilted over a range of angles to the beam direction. This enables control over the sidewall profile as well as radial uniformity optimisation. Ion beam directionality in conjunction with variable incident beam angle via platen angle setting enables profile control and feature shaping during nanopatterning. These hardware features unique to the Ion Beam etching methods can be used to create angled etch features. The CAIBE technique is also well suited to laser diode facet etch (for optoelectronic devices); these typically use III-V materials like InP. Here, we report on materials such as SiO2 etched without rotation and at a fixed platen angle allowing the formation of gratings and InP etched at a fixed angle with rotation allowing the formation of nanopillars and laser facets.

  2. Reactivity of surface of metal oxide particles: from adsorption of ions to deposition of colloidal particles

    International Nuclear Information System (INIS)

    Lefevre, Gregory

    2010-01-01

    In this Accreditation to supervise research (HDR), the author proposes an overview of his research works in the field of chemistry. These works more particularly addressed the understanding of the surface reactivity of metal oxide particles and its implication on sorption and adherence processes. In a first part, he addresses the study of surface acidity-alkalinity: measurement of surface reactivity by acid-base titration, stability of metal oxides in suspension, effect of morphology on oxide-hydroxide reactivity. The second part addresses the study of sorption: reactivity of iron oxides with selenium species, sorption of sulphate ions on magnetite, attenuated total reflection infrared spectroscopy (ATR-IR). Adherence effects are addressed in the third part: development of an experimental device to study adherence in massive substrates, deposition of particles under turbulent flow. The last part presents a research project on the effect of temperature on ion sorption at solids/solutions interfaces, and on the adherence of metal oxide particles. The author gives his detailed curriculum, and indicates his various publications, teaching activities, research and administrative responsibilities

  3. Chemically Induced Phase Transformation in Austenite by Focused Ion Beam

    Science.gov (United States)

    Basa, Adina; Thaulow, Christian; Barnoush, Afrooz

    2014-03-01

    A highly stable austenite phase in a super duplex stainless steel was subjected to a combination of different gallium ion doses at different acceleration voltages. It was shown that contrary to what is expected, an austenite to ferrite phase transformation occurred within the focused ion beam (FIB) milled regions. Chemical analysis of the FIB milled region proved that the gallium implantation preceded the FIB milling. High resolution electron backscatter diffraction analysis also showed that the phase transformation was not followed by the typical shear and plastic deformation expected from the martensitic transformation. On the basis of these observations, it was concluded that the change in the chemical composition of the austenite and the local increase in gallium, which is a ferrite stabilizer, results in the local selective transformation of austenite to ferrite.

  4. Thermal, chemical and spectral equilibration in heavy-ion collisions

    Energy Technology Data Exchange (ETDEWEB)

    Almási, Gábor András, E-mail: g.almasi@gsi.de [Gesellschaft für Schwerionenforschung, GSI, D-64291 Darmstadt (Germany); Wolf, György, E-mail: wolf.gyorgy@wigner.mta.hu [Wigner RCP, Budapest (Hungary)

    2015-11-15

    We have considered the equilibration in relativistic heavy ion collisions at energies 1–7 A GeV using our transport model. We applied periodic boundary conditions to close the system in a box. We found that the thermal equilibration takes place in the first 20–40 fm/c whose time is comparable to the duration of a heavy ion collision. The chemical equilibration is a much slower process and the system does not equilibrate in a heavy ion collision. We have shown that in the testparticle simulation of the Boltzmann equation the mass spectra of broad resonances follow instantaneously their in-medium spectral functions as expected from the Markovian approximation to the Kadanoff–Baym equations employed via the (local) gradient expansion.

  5. Spatially resolved images of reactive ions in the Orion Bar,★★.

    Science.gov (United States)

    Goicoechea, Javier R; Cuadrado, Sara; Pety, Jérôme; Bron, Emeric; Black, John H; Cernicharo, José; Chapillon, Edwige; Fuente, Asunción; Gerin, Maryvonne

    2017-05-01

    We report high angular resolution (4.9″×3.0″) images of reactive ions SH + , HOC + , and SO + toward the Orion Bar photodissociation region (PDR). We used ALMA-ACA to map several rotational lines at 0.8 mm, complemented with multi-line observations obtained with the IRAM 30 m telescope. The SH + and HOC + emission is restricted to a narrow layer of 2″- to 10″-width (≈800 to 4000 AU depending on the assumed PDR geometry) that follows the vibrationally excited [Formula: see text] emission. Both ions efficiently form very close to the H/H 2 transition zone, at a depth of A v ≲1 mag into the neutral cloud, where abundant C + , S + , and [Formula: see text] coexist. SO + peaks slightly deeper into the cloud. The observed ions have low rotational temperatures ( T rot ≈10-30 K≪ T k ) and narrow line-widths (~2-3 km s -1 ), a factor of ≃2 narrower that those of the lighter reactive ion CH + . This is consistent with the higher reactivity and faster radiative pumping rates of CH + compared to the heavier ions, which are driven relatively faster toward smaller velocity dispersion by elastic collisions and toward lower T rot by inelastic collisions. We estimate column densities and average physical conditions from an excitation model ( n (H 2 )≈10 5 -10 6 cm -3 , n ( e - )≈10 cm -3 , and T k ≈200 K). Regardless of the excitation details, SH + and HOC + clearly trace the most exposed layers of the UV-irradiated molecular cloud surface, whereas SO + arises from slightly more shielded layers.

  6. Dry fabrication of microdevices by the combination of focused ion beam and cryogenic deep reactive ion etching

    International Nuclear Information System (INIS)

    Chekurov, N; Tittonen, I; Grigoras, K; Sainiemi, L; Franssila, S; Peltonen, A

    2010-01-01

    In this paper, we demonstrate silicon microdevice fabrication by a combination of focused ion beam (FIB) and cryogenic deep reactive ion etching (DRIE). Applying FIB treatment only to a thin surface layer enables very high writing speed compared with FIB milling. The use of DRIE then defines the micro- and nanodevices utilizing the FIB-modified silicon as a mask. We demonstrate the ability to create patterns on highly 3D structures, which is extremely challenging by other nanofabrication methods. The alignment of optically made and FIB-defined patterns is also demonstrated. We also show that complete microelectromechanical systems (MEMS) can be fabricated by this method by presenting a double-ended tuning fork resonator as an example. Extremely short process time is achieved as the full fabrication cycle from mask design to electrical measurements can be completed during one working day.

  7. 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)

  8. Coal structure and reactivity changes induced by chemical demineralisation

    Energy Technology Data Exchange (ETDEWEB)

    Rubiera, F.; Arenillas, A.; Pevida, C.; Garcia, R.; Pis, J.J. [Department of Energy and Environment, Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain); Steel, K.M.; Patrick, J.W. [Fuel Technology Group, School of Chemical, Environmental and Mining Engineering, Nottingham University, University Park, NG7 2RD Nottingham (United Kingdom)

    2002-12-01

    The aim of this work was to determine the influence that an advanced demineralisation procedure has on the combustion characteristics of coal. A high-volatile bituminous coal with 6.2% ash content was treated in a mixture of hydrofluoric and fluorosilicic acids (HF/H{sub 2}SiF{sub 6}). Nitric acid was used either as a pretreatment, or as a washing stage after HF/H{sub 2}SiF{sub 6} demineralisation, with an ash content as low as 0.3% being attained in the latter case. The structural changes produced by the chemical treatment were evaluated by comparison of the FTIR spectra of the raw and treated coal samples. The devolatilisation and combustibility behaviour of the samples was studied by using a thermobalance coupled to a mass spectrometer (TGA-MS) for evolved gas analysis. The combustibility characteristics of the cleaned samples were clearly improved, there being a decrease in SO{sub 2} emissions.

  9. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  10. Ion implantation induced structural changes in reactively sputtered Cr-N layers on Si substrates

    International Nuclear Information System (INIS)

    Novakovic, M.; Popovic, M.; Perusko, D.; Milinovic, V.; Radovic, I.; Bibic, N.; Mitric, M.; Milosavljevic, M.

    2007-01-01

    This paper presents a study of the structure and composition of reactively sputtered Cr-N layers as a function of deposition parameters, and the effects of ion implantation on these structures. The layers were deposited on (1 0 0) Si substrates to a thickness of 240-280 nm, at different nitrogen partial pressure, and subsequently irradiated with 120 keV Ar ions. Structural characterisation of the samples was performed with Rutherford backscattering spectroscopy, transmission electron microscopy and X-ray diffraction analysis. We also measured their electrical resistivity with a four point probe. It was found that the layers grow in form of columnar structures, and their composition, Cr 2 N or CrN, strongly depends on the nitrogen partial pressure during deposition. Ion irradiation induces local micro-structural changes, formation of nano-particles and defects, which can be nicely correlated to the measured electrical resistivity

  11. The fabrication of silicon nanostructures by local gallium implantation and cryogenic deep reactive ion etching

    International Nuclear Information System (INIS)

    Chekurov, N; Grigoras, K; Franssila, S; Tittonen, I; Peltonen, A

    2009-01-01

    We show that gallium-ion-implanted silicon serves as an etch mask for fabrication of high aspect ratio nanostructures by cryogenic plasma etching (deep reactive ion etching). The speed of focused ion beam (FIB) patterning is greatly enhanced by the fact that only a thin approx. 30 nm surface layer needs to be modified to create a mask for the etching step. Etch selectivity between gallium-doped and undoped material is at least 1000:1, greatly decreasing the mask erosion problems. The resolution of the combined FIB-DRIE process is 20 lines μm -1 with the smallest masked feature size of 40 nm. The maximum achieved aspect ratio is 15:1 (e.g. 600 nm high pillars 40 nm in diameter).

  12. Model of wet chemical etching of swift heavy ions tracks

    Science.gov (United States)

    Gorbunov, S. A.; Malakhov, A. I.; Rymzhanov, R. A.; Volkov, A. E.

    2017-10-01

    A model of wet chemical etching of tracks of swift heavy ions (SHI) decelerated in solids in the electronic stopping regime is presented. This model takes into account both possible etching modes: etching controlled by diffusion of etchant molecules to the etching front, and etching controlled by the rate of a reaction of an etchant with a material. Olivine ((Mg0.88Fe0.12)2SiO4) crystals were chosen as a system for modeling. Two mechanisms of chemical activation of olivine around the SHI trajectory are considered. The first mechanism is activation stimulated by structural transformations in a nanometric track core, while the second one results from neutralization of metallic atoms by generated electrons spreading over micrometric distances. Monte-Carlo simulations (TREKIS code) form the basis for the description of excitations of the electronic subsystem and the lattice of olivine in an SHI track at times up to 100 fs after the projectile passage. Molecular dynamics supplies the initial conditions for modeling of lattice relaxation for longer times. These simulations enable us to estimate the effects of the chemical activation of olivine governed by both mechanisms. The developed model was applied to describe chemical activation and the etching kinetics of tracks of Au 2.1 GeV ions in olivine. The estimated lengthwise etching rate (38 µm · h-1) is in reasonable agreement with that detected in the experiments (24 µm · h-1).

  13. 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.

  14. 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.

  15. Unifying principles of irreversibility minimization for efficiency maximization in steady-flow chemically-reactive engines

    International Nuclear Information System (INIS)

    Ramakrishnan, Sankaran; Edwards, Christopher F.

    2014-01-01

    Systems research has led to the conception and development of various steady-flow, chemically-reactive, engine cycles for stationary power generation and propulsion. However, the question that remains unanswered is: What is the maximum-efficiency steady-flow chemically-reactive engine architecture permitted by physics? On the one hand the search for higher-efficiency cycles continues, often involving newer processes and devices (fuel cells, carbon separation, etc.); on the other hand the design parameters for existing cycles are continually optimized in response to improvements in device engineering. In this paper we establish that any variation in engine architecture—parametric change or process-sequence change—contributes to an efficiency increase via one of only two possible ways to minimize total irreversibility. These two principles help us unify our understanding from a large number of parametric analyses and cycle-optimization studies for any steady-flow chemically-reactive engine, and set a framework to systematically identify maximum-efficiency engine architectures. - Highlights: • A unified thermodynamic model to study chemically-reactive engine architectures is developed. • All parametric analyses of efficiency are unified by two irreversibility-minimization principles. • Variations in internal energy transfers yield a net work increase that is greater than engine irreversibility reduced. • Variations in external energy transfers yield a net work increase that is lesser than engine irreversibility reduced

  16. 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

  17. Spatially-Resolved Ion Trajectory Measurements During Cl2 Reactive Ion Beam Etching and Ar Ion Beam Etching

    International Nuclear Information System (INIS)

    Vawter, G. Allen; Woodworth, Joseph R.; Zubrzycki, Walter J.

    1999-01-01

    The angle of ion incidence at the etched wafer location during RIBE and IBE using Cl 2 , Ar and O 2 ion beams has been characterized using an ion energy and angle analyzer. Effects of beam current and accelerator grid bias on beam divergence and the spatial uniformity of the spread of incident angles are measured. It is observed that increased total beam current can lead to reduced current density at the sample stage due to enhanced beam divergence at high currents. Results are related to preferred etch system design for uniform high-aspect-ratio etching across semiconductor wafers

  18. A new concept for spatially divided Deep Reactive Ion Etching with ALD-based passivation

    International Nuclear Information System (INIS)

    Roozeboom, F; Kniknie, B; Lankhorst, A M; Winands, G; Knaapen, R; Smets, M; Poodt, P; Dingemans, G; Keuning, W; Kessels, W M M

    2012-01-01

    Conventional Deep Reactive Ion Etching (DRIE) is a plasma etch process with alternating half-cycles of 1) Si-etching with SF 6 to form gaseous SiF x etch products, and 2) passivation with C 4 F 8 that polymerizes as a protecting fluorocarbon deposit on the sidewalls and bottom of the etched features. In this work we report on a novel alternative and disruptive technology concept of Spatially-divided Deep Reactive Ion Etching, S-DRIE, where the process is converted from the time-divided into the spatially divided regime. The spatial division can be accomplished by inert gas bearing 'curtains' of heights down to ∼20 μm. These curtains confine the reactive gases to individual (often linear) injection slots constructed in a gas injector head. By horizontally moving the substrate back and forth under the head one can realize the alternate exposures to the overall cycle. A second improvement in the spatially divided approach is the replacement of the CVD-based C 4 F 8 passivation steps by ALD-based oxide (e.g. SiO 2 ) deposition cycles. The method can have industrial potential in cost-effective creation of advanced 3D interconnects (TSVs), MEMS manufacturing and advanced patterning, e.g., in nanoscale transistor line edge roughness using Atomic Layer Etching.

  19. Fabrication of antireflective nanostructures for crystalline silicon solar cells by reactive ion etching

    International Nuclear Information System (INIS)

    Lin, Hsin-Han; Chen, Wen-Hua; Wang, Chi-Jen; Hong, Franklin Chau-Nan

    2013-01-01

    In this study we have fabricated large-area (15 × 15 cm 2 ) subwavelength antireflection structure on poly-Si substrates to reduce their solar reflectivity. A reactive ion etching system was used to fabricate nanostructures on the poly-silicon surface. Reactive gases, composed of chlorine (Cl 2 ), sulfur hexafluoride (SF 6 ) and oxygen (O 2 ), were activated to fabricate nanoscale pyramids by RF plasma. The poly-Si substrates were etched in various gas compositions for 6–10 min to form nano-pyramids. The sizes of pyramids were about 200–300 nm in heights and about 100 nm in width. Besides the nanoscale features, the high pyramid density on the poly-Si surface is another important factor to reduce the reflectivity. Low-reflectivity surface was fabricated with reflectivity significantly reduced down to < 2% for photons in a wavelength range of 500–900 nm. - Highlights: ► Large-area (15 × 15 cm 2 ) antireflection structures fabricated on poly-Si substrates ► Si nano-pyramids produced by utilizing self-masked reactive ion etching process ► High density of nanoscale pyramids was formed on the entire substrate surface. ► Surface reflectivity below 2% was achieved in the wavelength range of 500–900 nm

  20. Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling

    International Nuclear Information System (INIS)

    Yekeler, Hulya; Yekeler, Meftuni

    2004-01-01

    The most commonly used collectors for sulfide minerals in the mining industry are the thiol collectors for the recovery of these minerals from their associated gangues by froth flotation. For this reason, a great deal of attention has been paid to understand the attachment mechanism of thiol collectors to metal sulfide surfaces. The density functional theory (DFT) calculations at the B3LYP/3-21G* and B3LYP/6-31++G** levels were employed to propose the flotation responses of these thiol collectors, namely, diethyl dithiocarbamate, ethyl dithiocarbamate, ethyl dithiocarbonate, ethyl trithiocarbonate and ethyl dithiophosphate ions, and to study the interaction energies of these collectors with Ag (+1) ion in connection to acanthite (Ag 2 S) mineral. The calculated interaction energies, ΔE, were interpreted in terms of the highest occupied molecular orbital (HOMO) energies of the isolated collector ions. The results show that the HOMOs are strongly localized to the sulfur atoms and the HOMO energies can be used as a reactivity descriptor for the flotation ability of the thiol collectors. Using the HOMO and ΔE energies, the reactivity order of the collectors is found to be (C 2 H 5 ) 2 NCS 2 - > C 2 H 5 NHCS 2 - > C 2 H 5 OCS 2 - > C 2 H 5 SCS 2 - > (C 2 H 5 O)(OH)PS 2 - . The theoretically obtained results are in good agreement with the experimental data reported

  1. Heavy ion measurements by use of chemical detectors

    International Nuclear Information System (INIS)

    Huebner, K.; Erzgraeber, G.; Eichhorn, K.

    1980-01-01

    In order to test whether the threshold system polyvinyl alcohol/methyl organe/chloral hydrate/sodium tetraborate permits quantitative detection of individual particles, the chemical detector was irradiated at the JINR U-200 cyclotron with 4 He, 12 C, 18 O, 22 Ne ions having different LET. Irradiations were performed with detectors of four different borax concentrations (the chloral hydrate concentration being constant). The colour change dose Dsub(u) increases linearly with increasing borax concentration and at constant borax concentration with increasing LET. Hence it follows that the G value of dehydrochlorination decreases with increasing LET. Fluence ranges measurable with detectors of different composition are given for the heavy ions studied. (author)

  2. 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

  3. 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)

  4. Silicon germanium as a novel mask for silicon deep reactive ion etching

    KAUST Repository

    Serry, Mohamed Y.

    2013-10-01

    This paper reports on the use of p-type polycrystalline silicon germanium (poly-Si1-xGex) thin films as a new masking material for the cryogenic deep reactive ion etching (DRIE) of silicon. We investigated the etching behavior of various poly-Si1-xGex:B (01:800). Furthermore, the SiGe mask was etched in SF6/O2 plasma at temperatures ≥ - 80°C and at rates exceeding 8 μm/min (i.e., more than 37 times faster than SiO2 or SiN masks). Because of the chemical and thermodynamic stability of the SiGe film as well as the electronic properties of the mask, it was possible to deposit the proposed film at CMOS backend compatible temperatures. The paper also confirms that the mask can easily be dry-removed after the process with high etching-rate by controlling the ICP and RF power and the SF6 to O2 ratios, and without affecting the underlying silicon substrate. Using low ICP and RF power, elevated temperatures (i.e., > - 80°C), and an adjusted O2:SF6 ratio (i.e., ~6%), we were able to etch away the SiGe mask without adversely affecting the final profile. Ultimately, we were able to develop deep silicon- trenches with high aspect ratio etching straight profiles. © 1992-2012 IEEE.

  5. Knudsen and inverse Knudsen layer effect on tail ion distribution and fusion reactivity in inertial confinement fusion targets

    Science.gov (United States)

    McDevitt, C. J.; Tang, X.-Z.; Guo, Z.; Berk, H. L.

    2014-10-01

    A series of reduced models are used to study the fast ion tail in the vicinity of a transition layer between plasmas at disparate temperatures and densities, which is typical of the gas-pusher interface in inertial confinement fusion targets. Emphasis is placed on utilizing progressively more comprehensive models in order to identify the essential physics for computing the fast ion tail at energies comparable to the Gamow peak. The resulting fast ion tail distribution is subsequently used to compute the fusion reactivity as a function of collisionality and temperature. It is found that while the fast ion distribution can be significantly depleted in the hot spot, leading to a reduction of the fusion reactivity in this region, a surplus of fast ions is present in the neighboring cold region. The presence of this fast ion surplus in the neighboring cold region is shown to lead to a partial recovery of the fusion yield lost in the hot spot.

  6. 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

  7. RICE: a computer program for multicomponent chemically reactive flows at all speeds

    International Nuclear Information System (INIS)

    Rivard, W.C.; Farmer, O.A.; Butler, T.D.

    1974-11-01

    The fluid dynamics of chemically reactive mixtures are calculated at arbitrary flow speeds with the RICE program. The dynamics are governed by the two-dimensional, time-dependent Navier-Stokes equations together with the species transport equations and the mass-action rate equations for the chemical reactions. The mass and momentum equations for the mixture are solved implicitly by the ICE technique. The equations for total energy and species transport are solved explicitly while the chemical rate equations are solved implicitly with a time step that may be a submultiple of the hydrodynamic time step. Application is made to continuous wave HF chemical lasers to compute the supersonic mixing and chemical reactions that take place in the lasing cavity. (U.S.)

  8. A Study of Moroccan Pupils' Difficulties at Second Baccalaureate Year in Solving Chemistry Problems Relating to the Reactivity of Ethanoate Ions and to Copper-Aluminium Cells

    Science.gov (United States)

    Ouasri, Ali

    2017-01-01

    This paper investigates the difficulties that Moroccan pupils (18-19) of the second Baccalaureate year encountered in solving chemical equilibrium problems relating to ethanoate ions' reactivity with water and methanoic acid, and to copper-aluminum cells. The pupils were asked to provide answers to questions derived from two problems. The…

  9. 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

  10. Formation of metal nanoparticles by short-distance sputter deposition in a reactive ion etching chamber

    International Nuclear Information System (INIS)

    Nie Min; Meng, Dennis Desheng; Sun Kai

    2009-01-01

    A new method is reported to form metal nanoparticles by sputter deposition inside a reactive ion etching chamber with a very short target-substrate distance. The distribution and morphology of nanoparticles are found to be affected by the distance, the ion concentration, and the sputtering time. Densely distributed nanoparticles of various compositions were fabricated on the substrates that were kept at a distance of 130 μm or smaller from the target. When the distance was increased to 510 μm, island structures were formed, indicating the tendency to form continuous thin film with longer distance. The observed trend for nanoparticle formation is opposite to the previously reported mechanism for the formation of nanoparticles by sputtering. A new mechanism based on the seeding effect of the substrate is proposed to interpret the experimental results.

  11. The reactivity study of peptide A3-capped gold and silver nanoparticles with heavy metal ions

    International Nuclear Information System (INIS)

    Yang, Hongyu; Tang, Zhenghua; Wang, Likai; Zhou, Weijia; Li, Ligui; Zhang, Yongqing; Chen, Shaowei

    2016-01-01

    Highlights: • Apparent color change upon the addition of Hg"2"+ or As"3"+ ions into A3-AuNPs solution. • Distinct color change of A3-AgNPs solution only in the presence of Hg"2"+ ions. • The Hg"2"+ concentration limit of A3-AgNPs about 40 times lower than A3-AuNPs. • Based on the DLS, TEM and XPS results, two reaction mechanisms have been proposed. - Abstract: Peptide A3-capped gold and silver nanoparticles were prepared by chemical reduction of metal salt precursors. The nanoparticles exhibited apparent but distinctly different color changes upon the addition of selected heavy metal ions. For gold nanoparticles, the solution color was found to change from red to blue in the presence of Hg"2"+ or As"3"+ ions, accompanied with broadening and a red-shift of the surface plasmon resonance peak. In contrast, silver nanoparticles showed an apparent color change from yellow to colorless only in the presence of Hg"2"+, along with a blue-shift and diminishment of the surface plasmon resonance peak. The Hg"2"+ reaction concentration limit of silver nanoparticle was about 40 times lower than that of gold nanoparticle. Based on the dynamic light scattering, transmission electron microscopy and X-ray photoelectron spectroscopic results, the reaction mechanism has been proposed. Such a sensitive variation of the nanoparticle optical properties to selective ions might be exploited for ion detection for potential applications.

  12. Thermal chemical-mechanical reactive flow model of shock initiation in solid explosives

    International Nuclear Information System (INIS)

    Nicholls, A.L. III; Tarver, C.M.

    1998-01-01

    The three dimensional Arbitrary Lagrange Eulerian hydrodynamic computer code ALE3D with fully coupled thermal-chemical-mechanical material models provides the framework for the development of a physically realistic model of shock initiation and detonation of solid explosives. The processes of hot spot formation during shock compression, subsequent ignition of reaction or failure to react, growth of reaction in individual hot spots, and coalescence of reacting hot spots during the transition to detonation can now be modeled using Arrhenius chemical kinetic rate laws and heat transfer to propagate the reactive flow. This paper discusses the growth rates of reacting hot spots in HMX and TATB and their coalescence during shock to detonation transition. Hot spot deflagration rates are found to be fast enough to consume explosive particles less than 10 mm in diameter during typical shock duration times, but larger particles must fragment and create more reactive surface area in order to be rapidly consumed

  13. 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.

  14. 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

  15. Deep reactive ion etching of silicon moulds for the fabrication of diamond x-ray focusing lenses

    Science.gov (United States)

    Malik, A. M.; Fox, O. J. L.; Alianelli, L.; Korsunsky, A. M.; Stevens, R.; Loader, I. M.; Wilson, M. C.; Pape, I.; Sawhney, K. J. S.; May, P. W.

    2013-12-01

    Diamond is a highly desirable material for use in x-ray optics and instrumentation. However, due to its extreme hardness and resistance to chemical attack, diamond is difficult to form into a structure suitable for x-ray lenses. Refractive lenses are capable of delivering x-ray beams with nanoscale resolution. A moulding technique for the fabrication of diamond lenses is reported. High-quality silicon moulds were made using photolithography and deep reactive ion etching. The study of the etch process conducted to achieve silicon moulds with vertical sidewalls and minimal surface roughness is discussed. Issues experienced when attempting to deposit diamond into a high-aspect-ratio mould by chemical vapour deposition are highlighted. Two generations of lenses have been successfully fabricated using this transfer-moulding approach with significant improvement in the quality and performance of the optics observed in the second iteration. Testing of the diamond x-ray optics on the Diamond Light Source Ltd synchrotron B16 beamline has yielded a line focus of sub-micrometre width.

  16. Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling

    Energy Technology Data Exchange (ETDEWEB)

    Yekeler, Hulya; Yekeler, Meftuni

    2004-09-15

    The most commonly used collectors for sulfide minerals in the mining industry are the thiol collectors for the recovery of these minerals from their associated gangues by froth flotation. For this reason, a great deal of attention has been paid to understand the attachment mechanism of thiol collectors to metal sulfide surfaces. The density functional theory (DFT) calculations at the B3LYP/3-21G* and B3LYP/6-31++G** levels were employed to propose the flotation responses of these thiol collectors, namely, diethyl dithiocarbamate, ethyl dithiocarbamate, ethyl dithiocarbonate, ethyl trithiocarbonate and ethyl dithiophosphate ions, and to study the interaction energies of these collectors with Ag (+1) ion in connection to acanthite (Ag{sub 2}S) mineral. The calculated interaction energies, {delta}E, were interpreted in terms of the highest occupied molecular orbital (HOMO) energies of the isolated collector ions. The results show that the HOMOs are strongly localized to the sulfur atoms and the HOMO energies can be used as a reactivity descriptor for the flotation ability of the thiol collectors. Using the HOMO and {delta}E energies, the reactivity order of the collectors is found to be (C{sub 2}H{sub 5}){sub 2}NCS{sub 2}{sup -} > C{sub 2}H{sub 5}NHCS{sub 2}{sup -} > C{sub 2}H{sub 5}OCS{sub 2}{sup -} > C{sub 2}H{sub 5}SCS{sub 2}{sup -} > (C{sub 2}H{sub 5}O)(OH)PS{sub 2}{sup -}. The theoretically obtained results are in good agreement with the experimental data reported.

  17. 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.

  18. Silicon surface damage caused by reactive ion etching in fluorocarbon gas mixtures containing hydrogen

    International Nuclear Information System (INIS)

    Norstroem, H.; Blom, H.; Ostling, M.; Nylandsted Larsen, A.; Keinonen, J.; Berg, S.

    1991-01-01

    For selective etching of SiO 2 on silicon, gases or gas mixtures containing hydrogen are often used. Hydrogen from the glow discharge promotes the formation of a thin film polymer layer responsible for the selectivity of the etching process. The reactive ion etch (RIE) process is known to create damage in the silicon substrate. The influence of hydrogen on the damage and deactivation of dopants is investigated in the present work. The distribution of hydrogen in silicon, after different etching and annealing conditions have been studied. The influence of the RIE process on the charge carrier concentration in silicon has been investigated. Various analytical techniques like contact resistivity measurements, four point probe measurements, and Hall measurements have been used to determine the influence of the RIE process on the electrical properties of processed silicon wafers. The hydrogen profile in as-etched and post annealed wafers was determined by the 1 H( 15 N,αγ) 12 C nuclear reaction. The depth of the deactivated surface layer is discussed in terms of the impinging hydrogen ion energy, i.e., the possibility of H + ions to pick up an energy equal to the peak-to-peak voltage of the rf signal

  19. 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

  20. 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.

  1. 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)

  2. 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.

  3. Chemical composition of waterfall-induced air ions: Spectrometry vs. simulations

    Energy Technology Data Exchange (ETDEWEB)

    Parts, T.-E.; Luts, A. [Tartu Univ. (Estonia). Dept. of Environmental Physics; Laakso, L.; Hirsikko, A.; Groenholm, T.; Kulmala, M. [Helsinki Univ. (Finland). Dept. of Physical Sciences

    2007-07-01

    Our measurements of ion size distributions near a waterfall provided new evidence for a waterfall-induced modification of air ion sizes. The ion size spectrum near a waterfall permanently differs from that in ordinary tropospheric air. In this paper we investigated the near-waterfall air ions chemical nature in detail. We carried out a simulation series of air small negative ion evolution, proposing that falling water, as a new environmental component, increases the concentration of OH{sup -} cluster ions. The produced OH{sup -} ions were employed as an extra input for our ion evolution model. The presence of additional OH{sup -} ions resulted in a decrease of typically model-provided NO{sub 3}{sup -} and/or HSO{sub 4}{sup -} cluster ion concentrations and an increase of the abundance of HCO{sub 3}{sup -} cluster ions. Near the waterfall the latter ions became dominant in our simulations. (orig.)

  4. The reactivity study of peptide A3-capped gold and silver nanoparticles with heavy metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hongyu [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Tang, Zhenghua, E-mail: zhht@scut.edu.cn [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Wang, Likai; Zhou, Weijia; Li, Ligui [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Zhang, Yongqing [Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Chen, Shaowei, E-mail: shaowei@ucsc.edu [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064 (United States)

    2016-08-15

    Highlights: • Apparent color change upon the addition of Hg{sup 2+} or As{sup 3+} ions into A3-AuNPs solution. • Distinct color change of A3-AgNPs solution only in the presence of Hg{sup 2+} ions. • The Hg{sup 2+} concentration limit of A3-AgNPs about 40 times lower than A3-AuNPs. • Based on the DLS, TEM and XPS results, two reaction mechanisms have been proposed. - Abstract: Peptide A3-capped gold and silver nanoparticles were prepared by chemical reduction of metal salt precursors. The nanoparticles exhibited apparent but distinctly different color changes upon the addition of selected heavy metal ions. For gold nanoparticles, the solution color was found to change from red to blue in the presence of Hg{sup 2+} or As{sup 3+} ions, accompanied with broadening and a red-shift of the surface plasmon resonance peak. In contrast, silver nanoparticles showed an apparent color change from yellow to colorless only in the presence of Hg{sup 2+}, along with a blue-shift and diminishment of the surface plasmon resonance peak. The Hg{sup 2+} reaction concentration limit of silver nanoparticle was about 40 times lower than that of gold nanoparticle. Based on the dynamic light scattering, transmission electron microscopy and X-ray photoelectron spectroscopic results, the reaction mechanism has been proposed. Such a sensitive variation of the nanoparticle optical properties to selective ions might be exploited for ion detection for potential applications.

  5. 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...

  6. Response of the ionosphere to the injection of chemically reactive vapors

    International Nuclear Information System (INIS)

    Bernhardt, P.A.

    1976-05-01

    As a gas released in the ionosphere expands, it is rapidly cooled. When the vapor becomes sufficiently tenuous, it is reheated by collisions with the ambient atmosphere, and its flow is then governed by diffusive expansion. As the injected gas becomes well mixed with the plasma, a hole is created by chemical processes. In the case of diatomic hydrogen release, depression of the electron concentrations is governed by the charge exchange reaction between oxygen ions and hydrogen, producing positive hydroxyl ions. Hydroxyl ions rapidly react with the electron gas to produce excited oxygen and hydrogen atoms. Enhanced airglow emissions result from the transition of the excited atoms to lower energy states. The electron temperature in the depleted region rises sharply and this rise causes a thermal expansion of the plasma and a further reduction in the local plasma concentration

  7. Reactivity of two hydrate forms of europium(3) ethylenediaminetetraacetate in the processes of central ion substitution

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.

    1985-01-01

    Kinetics of central ion substitution in the system EuA - -Cu 2+ , where A 4- -ethylenediaminetetraacetate (pH 6.0, t=25-55 deg C), has been studied spectrophotometrically. It is shown, that the form EuA(H 2 O) 3 - is more reactive as compared with EuA(H 2 O) 2 - . It is found, that equilibrium constant of the process EuA(H 2 O) 3 - reversible EuA(H 2 O) 2 - (1) equals 1 at t=36.2 deg C. The values ΔH and ΔS of the process (1), constituting 13.0+-3.2 kJ/mol and 41.8+-5.5 J/molxdeg respectively, are calculated

  8. Reactive ion beam etching for microcavity surface emitting laser fabrication: technology and damage characterization

    International Nuclear Information System (INIS)

    Matsutani, A.; Tadokoro, T.; Koyama, F.; Iga, K.

    1993-01-01

    Reactive ion beam etching (RIBE) is an effective dry etching technique for the fabrication of micro-sized surface emitting (SE) lasers and optoelectronic devices. In this chapter, some etching characteristics for GaAs, InP and GaInAsP with a Cl 2 gas using an RIBE system are discussed. Micro-sized circular mesas including GaInAsP/InP multilayers with vertical sidewalls were fabricated. RIBE-induced damage in InP substrates was estimated by C-V and PL measurement. In addition, the removal of the induced damage by the second RIBE with different conditions for the InP wafer was proposed. The sidewall damage is characterized by photoluminescence emitted from the etched sidewall of a GaInAsP/InP DH wafer. (orig.)

  9. New Colloidal Lithographic Nanopatterns Fabricated by Combining Pre-Heating and Reactive Ion Etching

    Directory of Open Access Journals (Sweden)

    Cong Chunxiao

    2009-01-01

    Full Text Available Abstract We report a low-cost and simple method for fabrication of nonspherical colloidal lithographic nanopatterns with a long-range order by preheating and oxygen reactive ion etching of monolayer and double-layer polystyrene spheres. This strategy allows excellent control of size and morphology of the colloidal particles and expands the applications of the colloidal patterns as templates for preparing ordered functional nanostructure arrays. For the first time, various unique nanostructures with long-range order, including network structures with tunable neck length and width, hexagonal-shaped, and rectangular-shaped arrays as well as size tunable nanohole arrays, were fabricated by this route. Promising potentials of such unique periodic nanostructures in various fields, such as photonic crystals, catalysts, templates for deposition, and masks for etching, are naturally expected.

  10. Ultraviolet Laser Damage Dependence on Contamination Concentration in Fused Silica Optics during Reactive Ion Etching Process

    Directory of Open Access Journals (Sweden)

    Laixi Sun

    2018-04-01

    Full Text Available The reactive ion etching (RIE process of fused silica is often accompanied by surface contamination, which seriously degrades the ultraviolet laser damage performance of the optics. In this study, we find that the contamination behavior on the fused silica surface is very sensitive to the RIE process which can be significantly optimized by changing the plasma generating conditions such as discharge mode, etchant gas and electrode material. Additionally, an optimized RIE process is proposed to thoroughly remove polishing-introduced contamination and efficiently prevent the introduction of other contamination during the etching process. The research demonstrates the feasibility of improving the damage performance of fused silica optics by using the RIE technique.

  11. Metal ion reactive thin films using spray electrostatic LbL assembly.

    Science.gov (United States)

    Krogman, Kevin C; Lyon, Katharine F; Hammond, Paula T

    2008-11-20

    By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide. On the basis of results reported here, future work could extend this method to include other toxic soft-base ligands such as carbon monoxide, benzene, or organophosphate nerve agents.

  12. Chemical equilibrium relations used in the fireball model of relativistic heavy ion reactions

    International Nuclear Information System (INIS)

    Gupta, S.D.

    1978-01-01

    The fireball model of relativistic heavy-ion collision uses chemical equilibrium relations to predict cross sections for particle and composite productions. These relations are examined in a canonical ensemble model where chemical equilibrium is not explicitly invoked

  13. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  14. Reactive-ion etching of nylon fabric meshes using oxygen plasma for creating surface nanostructures

    International Nuclear Information System (INIS)

    Salapare, Hernando S.; Darmanin, Thierry; Guittard, Frédéric

    2015-01-01

    Graphical abstract: - Highlights: • Reactive-ion etching (RIE) is employed to nylon 6,6 fabrics to achieve surface texturing and improved wettability. • FTIR spectra of the treated samples exhibited decreased transmittance of amide and carboxylic acid groups due to etching. • Etching is enhanced for higher power plasma treatments and for samples with larger mesh sizes. • Decreased crystallinity was achieved after plasma treatment. • Higher power induced higher negative DC self-bias voltage on the samples that favored anisotropic and aggressive etching. - Abstract: A facile one-step oxygen plasma irradiation in reactive ion etching (RIE) configuration is employed to nylon 6,6 fabrics with different mesh sizes to achieve surface nanostructures and improved wettability for textile and filtration applications. To observe the effects of power and irradiation time on the samples, the experiments were performed using constant irradiation time in varying power and using constant power in varying irradiation times. Results showed improved wettability after the plasma treatment. The FTIR spectra of all the treated samples exhibited decreased transmittance of the amide and carboxylic acid groups due to surface etching. The changes in the surface chemistry are supported by the SEM data wherein etching and surface nanostructures were observed for the plasma-treated samples. The etching of the surfaces is enhanced for higher power plasma treatments. The thermal analysis showed that the plasma treatment resulted in decreased crystallinity. Surface chemistry showed that the effects of the plasma treatment on the samples have no significant difference for all the mesh sizes. However, surface morphology showed that the sizes of the surface cracks are the same for all the mesh sizes but samples with larger mesh sizes exhibited enhanced etching as compared to the samples with smaller mesh sizes. Higher power induced higher negative DC self-bias voltage on the samples that

  15. 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.

  16. Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

    DEFF Research Database (Denmark)

    Reynisson, J.; Wilbrandt, R.; Brinck, V.

    2002-01-01

    . The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening...... of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown...... triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties....

  17. 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

  18. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    Energy Technology Data Exchange (ETDEWEB)

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.

    1997-07-01

    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  19. Time-of-flight secondary ion mass spectrometry with energetic cluster ion impact ionization for highly sensitive chemical structure characterization

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, K., E-mail: k.hirata@aist.go.jp [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K.; Narumi, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)

    2013-11-01

    Energetic cluster ions with energies of the order of sub MeV or greater were applied to time-of-flight (TOF) secondary ion (SI) mass spectrometry. This gave various advantages including enhancement of SIs required for chemical structure characterization and prevention of charging effects in SI mass spectra for organic targets. We report some characteristic features of TOF SI mass spectrometry using energetic cluster ion impact ionization and discuss two future applications of it.

  20. Fabrication of electrocatalytic Ta nanoparticles by reactive sputtering and ion soft landing

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Moser, Trevor; Engelhard, Mark; Browning, Nigel D.; Laskin, Julia

    2016-11-07

    About 40 years ago, it was shown that tungsten carbide exhibits similar catalytic behavior to Pt for certain commercially relevant reactions, thereby suggesting the possibility of cheaper and earth-abundant substitutes for costly and rare precious metal catalysts. In this work, reactive magnetron sputtering of Ta in the presence of three model hydrocarbons (2-butanol, heptane, and m-xylene) combined with gas aggregation and ion soft landing was employed to prepare organic-inorganic hybrid nanoparticles (NPs) on surfaces for evaluation of catalytic activity and durability. The electro-catalytic behavior of the NPs supported on glassy carbon was evaluated in acidic aqueous solution by cyclic voltammetry. The Ta-heptane and Ta-xylene NPs were revealed to be active and robust toward promotion of the oxygen reduction reaction, an important process occurring at the cathode in fuel cells. In comparison, pure Ta and Ta-butanol NPs were essentially unreactive. Characterization techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were applied to probe how different sputtering conditions such as the flow rates of gases, sputtering current, and aggregation length affect the properties of the NPs. AFM images reveal the focused size of the NPs as well as their preferential binding along the step edges of graphite surfaces. In comparison, TEM images of the same NPs on carbon grids show that they bind randomly to the surface with some agglomeration but little coalescence. The TEM images also reveal morphologies with crystalline cores surrounded by amorphous regions for NPs formed in the presence of 2-butanol and heptane. In contrast, NPs formed in the presence of m-xylene are amorphous throughout. XPS spectra indicate that while the percentage of Ta, C, and O in the NPs varies depending on the sputtering conditions and hydrocarbon employed, the electron binding energies of the elements are similar

  1. Chemical Reactivity Testing for the National Spent Nuclear Fuel Program. Quality Assurance Project Plan

    International Nuclear Information System (INIS)

    Newsom, H.C.

    1999-01-01

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of Work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, QA-101PD, revision 1, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted

  2. Chemical Reactivity and Spectroscopy Explored From QM/MM Molecular Dynamics Simulations Using the LIO Code

    Directory of Open Access Journals (Sweden)

    Juan P. Marcolongo

    2018-03-01

    Full Text Available In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU, that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  3. Chemical reactivity and spectroscopy explored from QM/MM molecular dynamics simulations using the LIO code

    Science.gov (United States)

    Marcolongo, Juan P.; Zeida, Ari; Semelak, Jonathan A.; Foglia, Nicolás O.; Morzan, Uriel N.; Estrin, Dario A.; González Lebrero, Mariano C.; Scherlis, Damián A.

    2018-03-01

    In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU), that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  4. Wafer-Scale Hierarchical Nanopillar Arrays Based on Au Masks and Reactive Ion Etching for Effective 3D SERS Substrate

    Directory of Open Access Journals (Sweden)

    Dandan Men

    2018-02-01

    Full Text Available Two-dimensional (2D periodic micro/nanostructured arrays as SERS substrates have attracted intense attention due to their excellent uniformity and good stability. In this work, periodic hierarchical SiO2 nanopillar arrays decorated with Ag nanoparticles (NPs with clean surface were prepared on a wafer-scale using monolayer Au NP arrays as masks, followed by reactive ion etching (RIE, depositing Ag layer and annealing. For the prepared SiO2 nanopillar arrays decorated with Ag NPs, the size of Ag NPs was tuned from ca. 24 to 126 nanometers by controlling the deposition thickness of Ag film. Importantly, the SiO2 nanopillar arrays decorated with Ag NPs could be used as highly sensitive SERS substrate for the detection of 4-aminothiophenol (4-ATP and rhodamine 6G (R6G due to the high loading of Ag NPs and a very uniform morphology. With a deposition thickness of Ag layer of 30 nm, the SiO2 nanopillar arrays decorated with Ag NPs exhibited the best sensitive SERS activity. The excellent SERS performance of this substrate is mainly attributed to high-density “hotspots” derived from nanogaps between Ag NPs. Furthermore, this strategy might be extended to synthesize other nanostructured arrays with a large area, which are difficult to be prepared only via conventional wet-chemical or physical methods.

  5. Wafer-Scale Hierarchical Nanopillar Arrays Based on Au Masks and Reactive Ion Etching for Effective 3D SERS Substrate.

    Science.gov (United States)

    Men, Dandan; Wu, Yingyi; Wang, Chu; Xiang, Junhuai; Yang, Ganlan; Wan, Changjun; Zhang, Honghua

    2018-02-04

    Two-dimensional (2D) periodic micro/nanostructured arrays as SERS substrates have attracted intense attention due to their excellent uniformity and good stability. In this work, periodic hierarchical SiO₂ nanopillar arrays decorated with Ag nanoparticles (NPs) with clean surface were prepared on a wafer-scale using monolayer Au NP arrays as masks, followed by reactive ion etching (RIE), depositing Ag layer and annealing. For the prepared SiO₂ nanopillar arrays decorated with Ag NPs, the size of Ag NPs was tuned from ca. 24 to 126 nanometers by controlling the deposition thickness of Ag film. Importantly, the SiO₂ nanopillar arrays decorated with Ag NPs could be used as highly sensitive SERS substrate for the detection of 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) due to the high loading of Ag NPs and a very uniform morphology. With a deposition thickness of Ag layer of 30 nm, the SiO₂ nanopillar arrays decorated with Ag NPs exhibited the best sensitive SERS activity. The excellent SERS performance of this substrate is mainly attributed to high-density "hotspots" derived from nanogaps between Ag NPs. Furthermore, this strategy might be extended to synthesize other nanostructured arrays with a large area, which are difficult to be prepared only via conventional wet-chemical or physical methods.

  6. Ion Internal Excitation and Co++ 2 Reactivity: Effect On The Titan, Mars and Venus Ionospheric Chemistry

    Science.gov (United States)

    Nicolas, C.; Zabka, J.; Thissen, R.; Dutuit, O.; Alcaraz, C.

    In planetary ionospheres, primary molecular and atomic photoions can be produced with substantial electronic and vibrational internal energy. In some cases, this is known to strongly affect both the rate constants and the branching ratio between the reac- tion products. A previous experimental study (Nicolas et al.) made at the Orsay syn- chrotron radiation facility has shown that many endothermic charge transfer reactions which were not considered in the ionospheric chemistry models of Mars, Venus and Earth have to be included because they are driven by electronic excitation of the parent ions. New measurements on two important reactions for Titan and Mars ionospheres, N+ + CH4 and O+ + CO2, will be presented. Branching ratios between products are very different when the parent atomic ions are prepared in their ground states, N+(3P) and O+(4S), or in their first electronic metastable states N+(1D) and O+(2D or P). 2 As the lifetime of these states are long enough, they survive during the mean time be- tween two collisions in the ionospheric conditions. So, the reactions of these excited states must be included in the ionospheric models. Absolute cross section measurements of the reactivity of stable doubly charged molec- ular ions CO++ and their implications for the Martian ionosphere will also be pre- 2 sented. The molecular dication CO++ production by VUV photoionisation and elec- 2 tron impact in the upper ionosphere of Mars is far from being negligible. However, to determine its concentration, it was necessary to evaluate the major loss channels of these ions. For this purpose, we measured the absolute reaction cross section of the sta- ble dications with CO2, the major neutral species of the Mars ionosphere. CO++ ions 2 were produced either by photoionisation or by electron impact, and a reaction cross section of 45 Å2 with 13CO2 was measured. The reaction leads to charge transfer or to collision induced dissociation. These results were integrated in a model

  7. Investigation of reactive-ion-etch-induced damage of InP/InGaAs multiple quantum wells by photoluminescence

    DEFF Research Database (Denmark)

    Steffensen, O. M.; Birkedal, Dan; Hanberg, J.

    1995-01-01

    The effects of CH4/H2 reactive ion etching (RIE) on the optical properties of an InP/InGaAs multiple-quantum-well structure have been investigated by low-temperature photoluminescence (PL). The structure consisted of eight InGaAs quantum wells, lattice matched to InP, with nominal thicknesses of 0...

  8. The influence of condensed tannin structure on rate of microbial mineralization and reactivity to chemical assays.

    Science.gov (United States)

    Norris, Charlotte E; Preston, Caroline M; Hogg, Karen E; Titus, Brian D

    2011-03-01

    We examined how tannin structure influences reactivity in tannin assays and carbon and nitrogen mineralization. Condensed tannins from the foliage of ten tree and shrub species and from pecan shells (Carya illinoensis) had different proportions of: (a) epicatechin (cis) and catechin (trans) isomers, (b) procyanidin (PC) and prodelphinidin (PD) monomers, and (c) different chain lengths. The response of each tannin to several widely used tannin assays was determined. Although there was some variation in response to proanthocyanidin (butanol/HCl) and Folin Ciocalteu assays, we did not deduce any predictable relationship between tannin structure and response to either assay. There was little variation in protein precipitation among the different tannins. To assess biological activity, six of the tannins were incubated with forest humus for 22 days. We determined that, while PC-based tannins remained at least partly extractable for the duration of the incubation, tannins with a high proportion of PD subunits rapidly became unextractable from soil. There was a positive correlation between net nitrogen mineralization and cis chemical structure. Carbon mineralization was enhanced initially by the addition of tannins to humus, but after 22 days, a negative correlation between the proportion of cis subunits and respiration was determined. Overall, we were not able to demonstrate consistent effects of structure on either microbial mineralization or reactivity to chemical assays; such relationships remain elusive.

  9. Chemical changes in titanate surfaces induced by Ar+ ion bombardment

    International Nuclear Information System (INIS)

    Gonzalez-Elipe, A.R.; Fernandez, A.; Espinos, J.P.; Munuera, G.; Sanz, J.M.

    1992-01-01

    The reduction effects and compositional changes induced by 3.5 keV Ar + bombardment of several titanates (i.e. SrTiO 3 , Al 2 TiO 5 and NiTiO 3 ) have been quantitatively investigated by XPS. In all the samples studied here the original Ti 4+ species were reduced to lower oxidation states (i.e. Ti 3+ and Ti 2+ ), although to a lesser extent than in pure TiO 2 . On the contrary, whereas Sr 2+ and Al 3+ seem to remain unaffected by Ar + bombardment, in agreement with the behaviour of the respective oxides (i.e. SrO and Al 2 O 3 ), Ni 2+ appears more easily reducible to Ni o in NiTiO 3 than in NiO. In addition, other specific differences were observed between the titanates, which reveal the existence of interesting chemical effects related to the presence of the different counter-ions in the titanates. In the case of Al 2 TiO 5 , its Ar + -induced decomposition to form TiO 2 + Al 2 O 3 could be followed by XPS. (Author)

  10. 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

  11. Efficient modeling of reactive transport phenomena by a multispecies random walk coupled to chemical equilibrium

    International Nuclear Information System (INIS)

    Pfingsten, W.

    1996-01-01

    Safety assessments for radioactive waste repositories require a detailed knowledge of physical, chemical, hydrological, and geological processes for long time spans. In the past, individual models for hydraulics, transport, or geochemical processes were developed more or less separately to great sophistication for the individual processes. Such processes are especially important in the near field of a waste repository. Attempts have been made to couple at least two individual processes to get a more adequate description of geochemical systems. These models are called coupled codes; they couple predominantly a multicomponent transport model with a chemical reaction model. Here reactive transport is modeled by the sequentially coupled code MCOTAC that couples one-dimensional advective, dispersive, and diffusive transport with chemical equilibrium complexation and precipitation/dissolution reactions in a porous medium. Transport, described by a random walk of multispecies particles, and chemical equilibrium calculations are solved separately, coupled only by an exchange term. The modular-structured code was applied to incongruent dissolution of hydrated silicate gels, to movement of multiple solid front systems, and to an artificial, numerically difficult heterogeneous redox problem. These applications show promising features with respect to applicability to relevant problems and possibilities of extensions

  12. 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, 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.

  13. 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.

  14. Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

    2015-06-15

    Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

  15. Deep reactive ion etching of auxetic structures: present capabilities and challenges

    International Nuclear Information System (INIS)

    Muslija, Alban; Díaz Lantada, Andrés

    2014-01-01

    Auxetic materials (or metamaterials) have negative Poisson ratios (NPR) and display the unexpected properties of lateral expansion when stretched, and equal and opposing densification when compressed. Such auxetic materials are being used more frequently in the development of novel products, especially in the fields of intelligent expandable actuators, shape-morphing structures and minimally invasive implantable devices. Although several micromanufacturing technologies have already been applied to the development of auxetic materials and devices, additional precision is needed to take full advantage of their special mechanical properties. In this study, we present a very promising approach for the development of auxetic materials and devices based on the use of deep reactive ion etching (DRIE). The process stands out for its precision and its potential applications to mass production. To our knowledge, it represents the first time this technology has been applied to the manufacture of auxetic materials with nanometric details. We take into account the present capabilities and challenges linked to the use of DRIE in the development of auxetic materials and auxetic-based devices. (technical note)

  16. Plasma diagnostics with electrostatic probes in the reactive low voltage ion plating process

    International Nuclear Information System (INIS)

    Lechleitner, T.; Huber, D.; Pulker, H.K.

    2002-01-01

    The analysis of cold plasmas, which are used in thin film coating techniques, is mainly important for the understanding of the correlation between the film properties and the plasma (or the process) parameters. With the knowledge of these correlations, one is able to optimise and eventually improve the coating processes for the production of films with certain desirable properties. The plasma for the reactive-low-voltage-ion-plating processes is a cold non-isothermal plasma produced by a low-pressure dc non-self sustained arc discharge, controlled by two main parameters, the arc current and the total gas pressure in the chamber. It was shown that the arc current is in a direct linear relation to the degree of ionization and the increase of the total gas pressure has a contrary effect. Besides, it was also demonstrated, that the usage of electrostatic probes for the plasma analysis od deposition processes is a powerful tool to complete the common plasma monitor measurements (energy analysing quadrupol mass spectrometer) and to improve the understanding of industrially used plasma. (nevyjel)

  17. In-situ reactive glow discharge cleaning of NSLS distributed ion pumps

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, E.D.; Chou, T.S.

    1988-01-01

    Based on our experience with the in-situ cleaning of optical systems by reactive r.f. glow discharges and the conditioning and preparation of distributed ion pump (DIP) elements, we have sought to develop strategies for recovering from severe vacuum accidents by restoring DIP elements of storage rings such as those at the NSLS in-situ. In this paper we will describe a series of experiments conducted in a test apparatus to condition a so called ''egg-crate'' DIP in-situ, (this older type element being common in older storage rings). A new untreated element which was unable to pump below 5x10 /sup /minus/8/ Torr in its initial condition was treated in oxygen and subsequent argon r.f. discharges utilizing the pump element as the discharge electrode producing a nitrogen pumping speed of 168 l/s at 2x10 /sup /minus/8/ Torr. A light bake at 75/degree/C increased this to nearly 500 l/s at 5x10 /sup /minus/8/ Torr. After exposure to atmosphere the speed was reduced to nil at these pressures but subsequently recovered, without bakeout, by glow discharge cleaning. 22 refs., 6 figs.

  18. The formation and reactivity of the μ+ molecular ion NeMu+

    International Nuclear Information System (INIS)

    Fleming, D.G.; Mikula, R.J.; Senba, M.; Garner, D.M.; Arseneau, D.J.

    1983-06-01

    Evidence for the formation and reactivity of the positive muon molecular ion NeMu + at room temperature in a low pressure Ne moderator to which trace amounts of Xe, CH 4 , NH 3 or He have been added, is reported. A two component relaxation of the diamagnetic muon spin rotation (μSR) signal is seen upon the addition of trace amounts of Xe to Ne; a fast relaxing component with bimolecular rate constant (3.6+-0.6) x 10 -10 cc atom -1 s -1 is thought to be due to thermal muonium formation in a charge exchange process while the other slow relaxing component is attributed to a muon transfer reaction, as in proton transfer studies. With CH 4 or NH 3 added to Ne there is, at most, only a very slow relaxation seen, even though thermal muonium formation is expected, in analogy with Xe. These latter results may be due to very fast, possibly tunneling-assisted, muon transfer reactions, the first time that such processes have been at all characterized

  19. The effect of reactive ion etch (RIE) process conditions on ReRAM device performance

    Science.gov (United States)

    Beckmann, K.; Holt, J.; Olin-Ammentorp, W.; Alamgir, Z.; Van Nostrand, J.; Cady, N. C.

    2017-09-01

    The recent surge of research on resistive random access memory (ReRAM) devices has resulted in a wealth of different materials and fabrication approaches. In this work, we describe the performance implications of utilizing a reactive ion etch (RIE) based process to fabricate HfO2 based ReRAM devices, versus a more unconventional shadow mask fabrication approach. The work is the result of an effort to increase device yield and reduce individual device size. Our results show that choice of RIE etch gas (SF6 versus CF4) is critical for defining the post-etch device profile (cross-section), and for tuning the removal of metal layers used as bottom electrodes in the ReRAM device stack. We have shown that etch conditions leading to a tapered profile for the device stack cause poor electrical performance, likely due to metal re-deposition during etching, and damage to the switching layer. These devices exhibit nonlinear I-V during the low resistive state, but this could be improved to linear behavior once a near-vertical etch profile was achieved. Device stacks with vertical etch profiles also showed an increase in forming voltage, reduced switching variability and increased endurance.

  20. Mercuric ions inhibit mitogen-activated protein kinase dephosphorylation by inducing reactive oxygen species

    International Nuclear Information System (INIS)

    Haase, Hajo; Engelhardt, Gabriela; Hebel, Silke; Rink, Lothar

    2011-01-01

    Mercury intoxication profoundly affects the immune system, in particular, signal transduction of immune cells. However, the mechanism of the interaction of mercury with cellular signaling pathways, such as mitogen activated protein kinases (MAPK), remains elusive. Therefore, the objective of this study is to investigate three potential ways in which Hg 2+ ions could inhibit MAPK dephosphorylation in the human T-cell line Jurkat: (1) by direct binding to phosphatases; (2) by releasing cellular zinc (Zn 2+ ); and (3) by inducing reactive oxygen species (ROS). Hg 2+ causes production of ROS, measured by dihydrorhodamine 123, and triggers ROS-mediated Zn 2+ release, detected with FluoZin-3. Yet, phosphatase-inhibition is not mediated by binding of Zn 2+ or Hg 2+ . Rather, phosphatases are inactivated by at least two forms of thiol oxidation; initial inhibition is reversible with reducing agents such as Tris(2-carboxyethyl)phosphine. Prolonged inhibition leads to non-reversible phosphatase oxidation, presumably oxidizing the cysteine thiol to sulfinic- or sulfonic acid. Notably, phosphatases are a particularly sensitive target for Hg 2+ -induced oxidation, because phosphatase activity is inhibited at concentrations of Hg 2+ that have only minor impact on over all thiol oxidation. This phosphatase inhibition results in augmented, ROS-dependent MAPK phosphorylation. MAPK are important regulators of T-cell function, and MAPK-activation by inhibition of phosphatases seems to be one of the molecular mechanisms by which mercury affects the immune system.

  1. In-situ reactive glow discharge cleaning of NSLS distributed ion pumps

    International Nuclear Information System (INIS)

    Johnson, E.D.; Chou, T.S.

    1988-01-01

    Based on our experience with the in-situ cleaning of optical systems by reactive r.f. glow discharges and the conditioning and preparation of distributed ion pump (DIP) elements, we have sought to develop strategies for recovering from severe vacuum accidents by restoring DIP elements of storage rings such as those at the NSLS in-situ. In this paper we will describe a series of experiments conducted in a test apparatus to condition a so called ''egg-crate'' DIP in-situ, (this older type element being common in older storage rings). A new untreated element which was unable to pump below 5x10 /sup /minus/8/ Torr in its initial condition was treated in oxygen and subsequent argon r.f. discharges utilizing the pump element as the discharge electrode producing a nitrogen pumping speed of 168 l/s at 2x10 /sup /minus/8/ Torr. A light bake at 75/degree/C increased this to nearly 500 l/s at 5x10 /sup /minus/8/ Torr. After exposure to atmosphere the speed was reduced to nil at these pressures but subsequently recovered, without bakeout, by glow discharge cleaning. 22 refs., 6 figs

  2. New chemical-DSMC method in numerical simulation of axisymmetric rarefied reactive flow

    Science.gov (United States)

    Zakeri, Ramin; Kamali Moghadam, Ramin; Mani, Mahmoud

    2017-04-01

    The modified quantum kinetic (MQK) chemical reaction model introduced by Zakeri et al. is developed for applicable cases in axisymmetric reactive rarefied gas flows using the direct simulation Monte Carlo (DSMC) method. Although, the MQK chemical model uses some modifications in the quantum kinetic (QK) method, it also employs the general soft sphere collision model and Stockmayer potential function to properly select the collision pairs in the DSMC algorithm and capture both the attraction and repulsion intermolecular forces in rarefied gas flows. For assessment of the presented model in the simulation of more complex and applicable reacting flows, first, the air dissociation is studied in a single cell for equilibrium and non-equilibrium conditions. The MQK results agree well with the analytical and experimental data and they accurately predict the characteristics of the rarefied flowfield with chemical reaction. To investigate accuracy of the MQK chemical model in the simulation of the axisymmetric flow, air dissociation is also assessed in an axial hypersonic flow around two geometries, the sphere as a benchmark case and the blunt body (STS-2) as an applicable test case. The computed results including the transient, rotational and vibrational temperatures, species concentration in the stagnation line, and also the heat flux and pressure coefficient on the surface are compared with those of the other chemical methods like the QK and total collision energy (TCE) models and available analytical and experimental data. Generally, the MQK chemical model properly simulates the chemical reactions and predicts flowfield characteristics more accurate rather than the typical QK model. Although in some cases, results of the MQK approaches match with those of the TCE method, the main point is that the MQK does not need any experimental data or unrealistic assumption of specular boundary condition as used in the TCE method. Another advantage of the MQK model is the

  3. Laser damage resistance of hafnia thin films deposited by electron beam deposition, reactive low voltage ion plating, and dual ion beam sputtering

    International Nuclear Information System (INIS)

    Gallais, Laurent; Capoulade, Jeremie; Natoli, Jean-Yves; Commandre, Mireille; Cathelinaud, Michel; Koc, Cian; Lequime, Michel

    2008-01-01

    A comparative study is made of the laser damage resistance of hafnia coatings deposited on fused silica substrates with different technologies: electron beam deposition (from Hf or HfO2 starting material), reactive low voltage ion plating, and dual ion beam sputtering.The laser damage thresholds of these coatings are determined at 1064 and 355 nm using a nanosecond pulsed YAG laser and a one-on-one test procedure. The results are associated with a complete characterization of the samples: refractive index n measured by spectrophotometry, extinction coefficient k measured by photothermal deflection, and roughness measured by atomic force microscopy

  4. Shallow nitrogen ion implantation: Evolution of chemical state and defect structure in titanium

    Energy Technology Data Exchange (ETDEWEB)

    Manojkumar, P.A., E-mail: manoj@igcar.gov.in [Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Chirayath, V.A.; Balamurugan, A.K.; Krishna, Nanda Gopala; Ilango, S.; Kamruddin, M.; Amarendra, G.; Tyagi, A.K. [Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Raj, Baldev [National Institute of Advanced Studies, Bangalore 560 012 (India)

    2016-09-15

    Highlights: • Low energy nitrogen ion implantation in titanium was studied. • Chemical and defect states were analyzed using SIMS, XPS and PAS. • SIMS and depth resolved XPS data showed good agreement. • Depth resolved defect and chemical states information were revealed. • Formation of 3 layers of defect states proposed to fit PAS results. - Abstract: Evolution of chemical states and defect structure in titanium during low energy nitrogen ion implantation by Plasma Immersion Ion Implantation (PIII) process is studied. The underlying process of chemical state evolution is investigated using secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The implantation induced defect structure evolution as a function of dose is elucidated using variable energy positron annihilation Doppler broadening spectroscopy (PAS) and the results were corroborated with chemical state. Formation of 3 layers of defect state was modeled to fit PAS results.

  5. 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.

  6. The chemical reactivity of the Martian soil and implications for future missions

    Science.gov (United States)

    Zent, Aaron P.; Mckay, Christopher P.

    1994-01-01

    Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

  7. 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.

  8. Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

    Science.gov (United States)

    Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

    2011-11-01

    Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

  9. Interaction of Hydroxyproline with Bivalent Metal Ions in Chemical ...

    African Journals Online (AJOL)

    NICO

    The stability constants of the ML and ML2 complex species of some metal ions, namely beryllium(II) and cobalt(II), with hydroxyproline were ... metal ions have several significant applications in biological systems.3–20 Beryllium is one ... 1 filter paper for chromatography was used for the purpose of electrophoresis. An Elico ...

  10. 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.

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

    Science.gov (United States)

    Scheeren, H. A.

    2003-09-01

    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 natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of

  12. Controlling line-edge roughness and reactive ion etch lag in sub-150 nm features in borophosphosilicate glass

    International Nuclear Information System (INIS)

    Bhatnagar, Parijat; Panda, Siddhartha; Edleman, Nikki L.; Allen, Scott D.; Wise, Richard; Mahorowala, Arpan

    2007-01-01

    We have developed a reactive ion etch (RIE) process in borophosphosilicate glass (BPSG) for 150 nm line-and-space features, where line-edge roughness (LER) complemented with RIE lag becomes a major issue. Effect of flow rates and carbon-to-fluorine atomic ratio of fluorohydrocarbon gases was utilized to achieve acceptable process window allowing lower radio frequency powers therefore obtaining acceptable LER and RIE lag in the high-resolution features etched into BPSG

  13. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    International Nuclear Information System (INIS)

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

    2015-01-01

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

  14. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Sudarjanto, Gatut [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller-Lehmann, Beatrice [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller, Jurg [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia)]. E-mail: j.keller@awmc.uq.edu.au

    2006-11-02

    The integrated chemical-biological degradation combining advanced oxidation by UV/H{sub 2}O{sub 2} followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H{sub 2}O{sub 2}/L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required.

  15. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    International Nuclear Information System (INIS)

    Sudarjanto, Gatut; Keller-Lehmann, Beatrice; Keller, Jurg

    2006-01-01

    The integrated chemical-biological degradation combining advanced oxidation by UV/H 2 O 2 followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H 2 O 2 /L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required

  16. Comparison of Electrocoagulation and Chemical Coagulation Processes in Removing Reactive red 196 from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Ali Assadi

    2016-06-01

    Full Text Available Background: Conventional chemical coagulation is considered as an old method to dye and COD removal in textile effluent. Electrocoagulation (EC process is a robust method to achieve maximum removal. Methods: This study was designed to compare the result of operational parameters including optimum pH and coagulant concentration for chemical coagulation with ferric chloride and alum also, voltage, electrolysis time, initial pH, and conductivity for EC with iron electrodes to remove reactive red 196 (RR 196. Results: The outcomes show that ferric chloride and alum at optimum concentration were capable of removing dye and COD by 79.63 % and 84.83% and 53% and 55%, respectively. In contrast, EC process removed the dye and COD by 99.98% and 90.4%, respectively. Conclusion: The highest treatment efficiency was obtained by increasing the voltage, electrolysis time, pH and conductivity. Increase initial dye concentration reduces removal efficiency. Ultimately, it could be concluded that EC technology is an efficient procedure for handling of colored industrial wastewaters.

  17. 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

  18. Chemical effects induced by ion implantation in molecular solids

    International Nuclear Information System (INIS)

    Foti, G.; Calcagno, L.; Puglisi, O.

    1983-01-01

    Ion implantation in molecular solids as ice, frozen noble gases, benzene and polymers produces a large amount of new molecules compared to the starting materials. Mass and energy analysis of ejected molecules together with the erosion yield, are discussed for several ion-target combinations at low temperature. The observed phenomena are analyzed in terms of deposited ennergy in electronic and nuclear collisions, for incoming beams, as helium or argon, in the range 10-2000 keV. (orig.)

  19. Multi-layered, chemically bonded lithium-ion and lithium/air batteries

    Science.gov (United States)

    Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

    2014-05-13

    Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

  20. Opto-chemical response of Makrofol-KG to swift heavy ion irradiation

    Indian Academy of Sciences (India)

    In the present study, the effects of swift heavy ion beam irradiation on the structural, chemical and optical properties of Makrofol solid-state nuclear track detector (SSNTD) were investigated. Makrofol-KG films of 40 m thickness were irradiated with oxygen beam (8+) with fluences ranging between 1010 ion/cm2 and 1012 ...

  1. A proposal for study of ion-beam induced chemical reactions using JAERI tandem accelerator

    International Nuclear Information System (INIS)

    1985-11-01

    Problems in ion-beam induced chemical reactions using JAERI Tandem Accelerator were discussed. Research philosophy, some proposed experiments which are based on measurements during ion-beam bombardment, and main features of the experimental apparatus are briefly described in this report. (author)

  2. 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.

  3. 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

  4. 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.

  5. Modeling of reactive chemical transport of leachates from a utility fly-ash disposal site

    International Nuclear Information System (INIS)

    Apps, J.A.; Zhu, M.; Kitanidis, P.K.; Freyberg, D.L.; Ronan, A.D.; Itakagi, S.

    1991-04-01

    Fly ash from fossil-fuel power plants is commonly slurried and pumped to disposal sites. The utility industry is interested in finding out whether any hazardous constituents might leach from the accumulated fly ash and contaminate ground and surface waters. To evaluate the significance of this problem, a representative site was selected for modeling. FASTCHEM, a computer code developed for the Electric Power Research Institute, was utilized for the simulation of the transport and fate of the fly-ash leachate. The chemical evolution of the leachate was modeled as it migrated along streamtubes defined by the flow model. The modeling predicts that most of the leachate seeps through the dam confining the ash pond. With the exception of ferrous, manganous, sulfate and small amounts of nickel ions, all other dissolved constituents are predicted to discharge at environmentally acceptable concentrations

  6. Preparation of composite micro/nano structure on the silicon surface by reactive ion etching: Enhanced anti-reflective and hydrophobic properties

    Science.gov (United States)

    Zeng, Yu; Fan, Xiaoli; Chen, Jiajia; He, Siyu; Yi, Zao; Ye, Xin; Yi, Yougen

    2018-05-01

    A silicon substrate with micro-pyramid structure (black silicon) is prepared by wet chemical etching and then subjected to reactive ion etching (RIE) in the mixed gas condition of SF6, CHF3 and He. We systematically study the impacts of flow rates of SF6, CHF3 and He, the etching pressure and the etching time on the surface morphology and reflectivity through various characterizations. Meanwhile, we explore and obtain the optimal combination of parameters for the preparation of composite structure that match the RIE process based on the basis of micro-pyramid silicon substrate. The composite sample prepared under the optimum parameters exhibits excellent anti-reflective performance, hydrophobic, self-cleaning and anti-corrosive properties. Based on the above characteristics, the composite micro/nano structure can be applied to solar cells, photodetectors, LEDs, outdoor devices and other important fields.

  7. Acetonitrile Chemical Ionization Ion Trap Mass Spectrometry of Chemical Warfare Agents and Their Degradation Products

    National Research Council Canada - National Science Library

    Rohrbaugh, Dennis

    1998-01-01

    .... The protonated molecular ion was observed as the dominant ion and base peak for HD, VX, GA, 1,4-dithiane, 2-diisopropylaminoethanol, and the trimethylsilyl derivatives of methylphosphonic acid...

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. Chemical modification of polypropylene induced by high energy carbon ions

    Energy Technology Data Exchange (ETDEWEB)

    Saha, A.; Chakraborty, V.; Chintalapudi, S.N. E-mail: snc@gamma.iuc.res.in

    2000-06-01

    Polypropylene was irradiated with {sup 12}C{sup +} ions of 3.6 and 5.4 MeV energy using 3 MV Pelletron. The spectral changes owing to ion bombardment were investigated by UV-VIS and Fourier-transform infrared (FTIR) spectroscopy. A gradual increase in absorbance was observed around visible and near visible region with increase in fluence of bombarding ions. The difference absorption spectra show formation of chromophoric groups with wavelength maximum near 380 nm at lower fluence, but at high fluence a shift in peak is observed. The chromophoric groups are likely to be the extended conjugated polyene system and the red shift in peak position at high fluence may be attributed to the greater degree of conjugation. The formation of unsaturated linkage is confirmed by the FTIR spectra with observed stretching band around 1650 cm{sup -1} and its intensity was found to increase with increase in ion fluence studied. The gases (in the range 2-80 amu) which were evolved due to interaction of polypropylene with {sup 12}C{sup +} ions were measured with Residual Gas Analyzer (RGA). A large number of gaseous components were detected. This shows that polymer chains break into some smaller fragments which concomitantly leads to extended conjugation.

  14. 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

  15. Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

    International Nuclear Information System (INIS)

    Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

    2002-01-01

    Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

  16. Treatment of radioactive wastewaters by chemical precipitation and ion exchange

    International Nuclear Information System (INIS)

    Robinson, S.M.; Begovich, J.M.; Brown, C.H. Jr.; Campbell, D.O.; Collins, E.D.

    1987-01-01

    Precipitation and ion exchange methods are being developed at Oak Ridge National Laboratory to decontaminate wastewaters containing small amounts of 90 Sr and 137 Cs while minimizing waste generation. Distribution coefficients have been determined for strontium and cesium as functions of Ca, Na, and Mg concentrations from bench- and pilot-scale data for ion exchange resins and zeolites using actual wastewaters. Models have been used to estimate the total amount of waste that would be generated at full-scale operation. Based on these data, four process flowsheets are being tested at full-scale. 14 refs., 8 figs., 7 tabs

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

    Energy Technology Data Exchange (ETDEWEB)

    Bratton, Robert Lawrence

    2002-04-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH_SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH_SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding. A

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

    International Nuclear Information System (INIS)

    Bratton, Robert Lawrence

    2002-01-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH( ) SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH( ) SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding

  19. Ion-beam induced chemical and structural modification in polymers

    Czech Academy of Sciences Publication Activity Database

    Guenther, M.; Gerlach, G.; Suchaneck, G.; Sahre, K.; Eichorn, K. J.; Wolf, B.; Deineka, Alexander; Jastrabík, Lubomír

    158-159, - (2002), s. 108-113 ISSN 0257-8972 Grant - others:Ge(DE) 779/6-1 Institutional research plan: CEZ:AV0Z1010914 Keywords : polyimide * polyethersulfone- hardness * conductivity * polymer structure * ion implantation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.267, year: 2002

  20. Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

    Directory of Open Access Journals (Sweden)

    Christelle Pau Ping Wong

    2015-10-01

    Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

  1. Analysis of abused drugs by selected ion monitoring: quantitative comparison of electron impact and chemical ionization

    International Nuclear Information System (INIS)

    Foltz, R.L.; Knowlton, D.A.; Lin, D.C.K.; Fentiman, A.F. Jr.

    1975-01-01

    A comparison was made of the relative sensitivities of electron impact and chemical ionization when used for selected ion monitoring analysis of commonly abused drugs. For most of the drugs examined chemical ionization using ammonia as the reactant gas gave the largest single m/e ion current response per unit weight of sample. However, if maximum sensitivity is desired it is important to evaluate electron impact and chemical ionization with respect to both maximum response and degree of interference from background and endogenous materials

  2. 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

  3. 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.

  4. Role of Chemical Reactivity and Transition State Modeling for Virtual Screening.

    Science.gov (United States)

    Karthikeyan, Muthukumarasamy; Vyas, Renu; Tambe, Sanjeev S; Radhamohan, Deepthi; Kulkarni, Bhaskar D

    2015-01-01

    Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product- like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

  5. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan

    2015-12-30

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  6. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  7. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Herng, Tun Seng; Aratani, Naoki; Goncalves, Theo; Qi, Qingbiao; Shi, Xueliang; Yamada, Hiroko; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2015-01-01

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  8. 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.)

  9. Change of chemical bond and wettability of polylacticacid implanted with high-flux carbon ion

    International Nuclear Information System (INIS)

    Zhang Jizhong; Kang Jiachen; Zhang Xiaoji; Zhou Hongyu

    2008-01-01

    Polylacticacid (PLA) was submitted to high-flux carbon ion implantation with energy of 40 keV. It was investigated to the effect of ion fluence (1 x 10 12 -1 x 10 15 ions/cm 2 ) on the properties of the polymer. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), wettability, and roughness were employed to study change of structure and properties of the as-implanted PLA samples. Six carbon bonds, that is, C, C-H, C-O-C, C-O, O-C-O, and >C=O, were observed on surfaces of the as-implanted PLA samples. The intensities of various chemical bonds changed with increasing ion fluence. AFM images displayed that there was irradiation damage and that it was related closely with ion fluence. At fluence as high as 1 x 10 15 ions/cm 2 surface-restructuring phenomenum took place on the surface of the PLA. Wettability was also affected by the variation on the fluence. With increasing ion fluence, the water contact angle of the as-implanted PLA samples changed gradually reaching a maximum of 76.5 deg. with 1 x 10 13 ions/cm 2 . The experimental results revealed that carbon ion fluence strongly affected surface chemical bond, morphology, wettability, and roughness of the PLA samples

  10. Underlying role of mechanical rigidity and topological constraints in physical sputtering and reactive ion etching of amorphous materials

    Science.gov (United States)

    Bhattarai, Gyanendra; Dhungana, Shailesh; Nordell, Bradley J.; Caruso, Anthony N.; Paquette, Michelle M.; Lanford, William A.; King, Sean W.

    2018-05-01

    Analytical expressions describing ion-induced sputter or etch processes generally relate the sputter yield to the surface atomic binding energy (Usb) for the target material. While straightforward to measure for the crystalline elemental solids, Usb is more complicated to establish for amorphous and multielement materials due to composition-driven variations and incongruent sublimation. In this regard, we show that for amorphous multielement materials, the ion-driven yield can instead be better understood via a consideration of mechanical rigidity and network topology. We first demonstrate a direct relationship between Usb, bulk modulus, and ion sputter yield for the elements, and then subsequently prove our hypothesis for amorphous multielement compounds by demonstrating that the same relationships exist between the reactive ion etch (RIE) rate and nanoindentation Young's modulus for a series of a -Si Nx :H and a -Si OxCy :H thin films. The impact of network topology is further revealed via application of the Phillips-Thorpe theory of topological constraints, which directly relates the Young's modulus to the mean atomic coordination () for an amorphous solid. The combined analysis allows the trends and plateaus in the RIE rate to be ultimately reinterpreted in terms of the atomic structure of the target material through a consideration of . These findings establish the important underlying role of mechanical rigidity and network topology in ion-solid interactions and provide additional considerations for the design and optimization of radiation-hard materials in nuclear and outer space environments.

  11. 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

  12. Chemical characterization of 4140 steel implanted by nitrogen ions

    International Nuclear Information System (INIS)

    Niño, E D V; Dugar-Zhabon, V; Pinto, J L; Henao, J A

    2012-01-01

    AISI SAE 4140 steel samples of different surface roughness which are implanted with 20 keV and 30 keV nitrogen ions at a dose of 10 17 ions/cm 2 are studied. The crystal phases of nitrogen compositions of the implanted samples, obtained with help of an x-ray diffraction method, are confronted with the data reported by the International Centre for Diffraction Data (ICDD) PDF-2. The implantation treatment is realized in high-voltage pulsed discharges at low pressures. The crystal structure of the implanted solid surfaces is analyzed by the x-ray diffraction technique which permits to identify the possible newly formed compounds and to identify any change in the surface structure of the treated samples. A decrease in the intensity of the plane (110), a reduction of the cell unity in values of 2-theta and a diminishing of the crystallite dimensions in comparison with non-implanted samples are observed.

  13. Chemical characterization of 4140 steel implanted by nitrogen ions

    Science.gov (United States)

    Niño, E. D. V.; Pinto, J. L.; Dugar-Zhabon, V.; Henao, J. A.

    2012-06-01

    AISI SAE 4140 steel samples of different surface roughness which are implanted with 20 keV and 30 keV nitrogen ions at a dose of 1017 ions/cm2 are studied. The crystal phases of nitrogen compositions of the implanted samples, obtained with help of an x-ray diffraction method, are confronted with the data reported by the International Centre for Diffraction Data (ICDD) PDF-2. The implantation treatment is realized in high-voltage pulsed discharges at low pressures. The crystal structure of the implanted solid surfaces is analyzed by the x-ray diffraction technique which permits to identify the possible newly formed compounds and to identify any change in the surface structure of the treated samples. A decrease in the intensity of the plane (110), a reduction of the cell unity in values of 2-theta and a diminishing of the crystallite dimensions in comparison with non-implanted samples are observed.

  14. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Waltman, Melanie J. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States)

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  15. Chemical characterization of 4140 steel implanted by nitrogen ions

    Energy Technology Data Exchange (ETDEWEB)

    Nino, Ely Dannier V.; Duran, Fernando [Grupo de Investigacion en Tecnologia del Plasma (GINTEP), Departamento de Ciencias Basicas, Universidad Pontificia Bolivariana, Bucaramanga (Colombia); Pinto, Jose L.C. [Grupo de Investigacion en Quimica Estructural (GIQUE), Universidad Industrial de Santander, Bucaramanga (Colombia); Dugar-Zhabon, V.; Garnica, Hernan [Grupo de Fisica y Tecnologia del Plasma (FITEK), Universidad Industrial de Santander, Bucaramanga (Colombia)

    2010-07-01

    AISI-SAE 4140 sample surfaces of different roughness which are implanted by nitrogen ions of 20 keV and 30 keV at a dose of 10{sup 17} ions/cm{sup 2} through a three dimensional ion implantation technique are studied. Crystal phases of nitrogen compositions of the implanted samples, obtained with help of an x-ray diffraction method, are confronted with the data reported by the International Centre for Diffraction Data (ICDD), PDF-2. It is observed that the implanted into the metal nitrogen atoms produce changes in orientation of crystal planes that is manifested as variations of the intensity of the refracted rays and of cell dimensions (a displacement of 2 theta of the maximum intensity position). An analysis for determining nitrogen atoms implanted by high-voltage pulsed discharges at low pressures in the crystal structure of the solid surface was carried out by X-Ray Diffraction due to this technique permits to assess the possibility of formation of new compounds. (author)

  16. Chemical characterization of 4140 steel implanted by nitrogen ions

    International Nuclear Information System (INIS)

    Nino, Ely Dannier V.; Duran, Fernando; Pinto, Jose L.C.; Dugar-Zhabon, V.; Garnica, Hernan

    2010-01-01

    AISI-SAE 4140 sample surfaces of different roughness which are implanted by nitrogen ions of 20 keV and 30 keV at a dose of 10"1"7 ions/cm"2 through a three dimensional ion implantation technique are studied. Crystal phases of nitrogen compositions of the implanted samples, obtained with help of an x-ray diffraction method, are confronted with the data reported by the International Centre for Diffraction Data (ICDD), PDF-2. It is observed that the implanted into the metal nitrogen atoms produce changes in orientation of crystal planes that is manifested as variations of the intensity of the refracted rays and of cell dimensions (a displacement of 2 theta of the maximum intensity position). An analysis for determining nitrogen atoms implanted by high-voltage pulsed discharges at low pressures in the crystal structure of the solid surface was carried out by X-Ray Diffraction due to this technique permits to assess the possibility of formation of new compounds. (author)

  17. 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)

  18. Studying Equilibrium in the Chemical Reaction between Ferric and Iodide Ions in Solution Using a Simple and Inexpensive Approach

    Science.gov (United States)

    Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

    2016-01-01

    A laboratory experiment on the study of the chemical equilibrium based on the reaction between ferric and iodide ions in solution with the formation of ferrous ions, free iodine, and triiodide ions is developed. The total concentration of iodide and triiodide ions in the reaction mixture during the reaction is determined by the argentometric…

  19. Sheath-lens probe for negative ion detection in reactive plasmas

    International Nuclear Information System (INIS)

    Stamate, E.; Sugai, H.; Takai, O.; Ohe, K.

    2004-01-01

    A method that allows easy and inexpensive detection of negative ions is introduced. The method is based upon the electrostatic lens effect of the sheath layer evolving to a positively biased planar probe that focuses the negative charges to distinct regions on the surface. Trajectories of negative ions inside the sheath are obtained after computing the potential and electric field distribution by solving in three dimensions the nonlinear Poisson equation. The negative ions' flux to square and disk probes is developed in Ar/SF 6 and O 2 plasmas. The method allows negative ion detection with sensitivity higher than that of Langmuir probes

  20. Multiple-height microstructure fabricated by deep reactive ion etching and soft resist masks combined with UV curing

    International Nuclear Information System (INIS)

    Sato, R; Sawada, T; Kumagai, S; Sasaki, M

    2014-01-01

    Multiple-height microstructures are realized by deep reactive ion etching and UV-cured photoresist used in the embedded mask process. Although the UV-cured photoresist is a soft mask, its material property becomes stable against resist thinner and UV exposure. A layered resist pattern can be realized by stacking normal photoresist on the UV-cured photoresist. The normal photoresist can be selectively removed by the flush exposure and developing after the first Si etching. This technique is applied to two MEMS devices

  1. High temperature reactive ion etching of iridium thin films with aluminum mask in CF4/O2/Ar plasma

    Directory of Open Access Journals (Sweden)

    Chia-Pin Yeh

    2016-08-01

    Full Text Available Reactive ion etching (RIE technology for iridium with CF4/O2/Ar gas mixtures and aluminum mask at high temperatures up to 350 °C was developed. The influence of various process parameters such as gas mixing ratio and substrate temperature on the etch rate was studied in order to find optimal process conditions. The surface of the samples after etching was found to be clean under SEM inspection. It was also shown that the etch rate of iridium could be enhanced at higher process temperature and, at the same time, very high etching selectivity between aluminum etching mask and iridium could be achieved.

  2. Sacrificial structures for deep reactive ion etching of high-aspect ratio kinoform silicon x-ray lenses

    DEFF Research Database (Denmark)

    Stöhr, Frederik; Michael-Lindhard, Jonas; Hübner, Jörg

    2015-01-01

    This article describes the realization of complex high-aspect ratio silicon structures with feature dimensions from 100 lm to 100nm by deep reactive ion etching using the Bosch process. As the exact shape of the sidewall profiles can be crucial for the proper functioning of a device, the authors...... of the sacrificial structures was accomplished by thermal oxidation and subsequent selective wet etching. The effects of the dimensions and relative placement of sacrificial walls and pillars on the etching result were determined through systematic experiments. The authors applied this process for exact sidewall...

  3. Status of chemical equilibrium in relativistic heavy-ion collisions

    Indian Academy of Sciences (India)

    Chemical equilibrium; particle multiplicities. PACS Nos 24.10.Pa; 25.75.Dw; 25.75.-q. 1. Introduction. In hydrodynamic models [1] the freeze-out surface is very sensitive on the initial condi- tions and is therefore ... not agree with a recent similar analysis of Pb–Pb data [12] imposing full strangeness equi- librium. The main ...

  4. 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.

  5. Drop drying on surfaces determines chemical reactivity - the specific case of immobilization of oligonucleotides on microarrays

    Science.gov (United States)

    2013-01-01

    Background Drop drying is a key factor in a wide range of technical applications, including spotted microarrays. The applied nL liquid volume provides specific reaction conditions for the immobilization of probe molecules to a chemically modified surface. Results We investigated the influence of nL and μL liquid drop volumes on the process of probe immobilization and compare the results obtained to the situation in liquid solution. In our data, we observe a strong relationship between drop drying effects on immobilization and surface chemistry. In this work, we present results on the immobilization of dye labeled 20mer oligonucleotides with and without an activating 5′-aminoheptyl linker onto a 2D epoxysilane and a 3D NHS activated hydrogel surface. Conclusions Our experiments identified two basic processes determining immobilization. First, the rate of drop drying that depends on the drop volume and the ambient relative humidity. Oligonucleotides in a dried spot react unspecifically with the surface and long reaction times are needed. 3D hydrogel surfaces allow for immobilization in a liquid environment under diffusive conditions. Here, oligonucleotide immobilization is much faster and a specific reaction with the reactive linker group is observed. Second, the effect of increasing probe concentration as a result of drop drying. On a 3D hydrogel, the increasing concentration of probe molecules in nL spotting volumes accelerates immobilization dramatically. In case of μL volumes, immobilization depends on whether the drop is allowed to dry completely. At non-drying conditions, very limited immobilization is observed due to the low oligonucleotide concentration used in microarray spotting solutions. The results of our study provide a general guideline for microarray assay development. They allow for the initial definition and further optimization of reaction conditions for the immobilization of oligonucleotides and other probe molecule classes to different

  6. Dissociation mechanism of HNIW ions investigated by chemical ionization and electron impact mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rongjie; Xiao, Hemiao [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

    2006-04-15

    Chemical Ionization (CI) with Collision-Induced Dissociation (CID) spectroscopy and Electron Impacting (EI) with metastable Mass analyzed Ion Kinetic Energy (MIKE) spectroscopy have been applied to study ionic dissociations of Hexanitrohexaazaisowurtzitane (HNIW). Similarities and differences between EI/MIKE and CI/CID mass spectra of HNIW were analyzed. In EI mass spectra, the ions [HNIW-n NO{sub 2}]{sup +} (n=2-5), such as the ion at m/z 347, were less frequent (1-2% relative abundance), but in CI mass spectra, these ions were very abundant. For some ions of large molar mass from HNIW, their dissociations pathways from parent ions to daughter ions were built according to CID and MIKE spectra. Molecular ions of HNIW with a protonated nitro group at five-member ring seem more stable than at six-member ring. The HNIW ions losing five of six nitro groups are very stable based on CID spectra, which agrees with some research results for thermal decomposition of HNIW in literature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  7. Ion exchange and adsorption in nuclear chemical engineering

    International Nuclear Information System (INIS)

    Schultz, W.W.; Wheelwright, E.J.; Godbee, H.; Mallory, C.W.; Burney, G.A.; Wallace, R.M.

    1983-01-01

    The nuclear industry involves a number of operations. Uranium ore must first be mined and the uranium recovered from the ore, purified, and concentrated. After the uranium has been enriched and fabricated into fuel elements, it is placed in nuclear reactors where it produces energy, fission products, and transmutation products. Finally, if the fuel cycle is completed, the uranium and useful transmutation products are recovered and separated from each other as well as from the fission products. The uranium may be recycled or used elsewhere, while most of the fission products become waste. Ion exchange finds use in nearly every part of the nuclear fuel cycle; these uses are the subject of this paper

  8. Structure and reactivity of molybdenum oxide cluster ions in the gas phase

    International Nuclear Information System (INIS)

    Goncharov, V.B.; Fialko, E.F.

    2002-01-01

    A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

  9. Deep reactive ion etching of fused silica using a single-coated soft mask layer for bio-analytical applications

    International Nuclear Information System (INIS)

    Ray, Tathagata; Zhu, Haixin; Meldrum, Deirdre R

    2010-01-01

    In this note, we present our results from process development and characterization of reactive ion etching (RIE) of fused silica using a single-coated soft masking layer (KMPR® 1025, Microchem Corporation, Newton, MA). The effects of a number of fluorine-radical-based gaseous chemistries, the gas flow rate, RF power and chamber pressure on the etch rate and etching selectivity of fused silica were studied using factorial experimental designs. RF power and pressure were found to be the most important factors in determining the etch rate. The highest fused silica etch rate obtained was about 933 Å min −1 by using SF 6 -based gas chemistry, and the highest etching selectivity between the fused silica and KMPR® 1025 was up to 1.2 using a combination of CF 4 , CHF 3 and Ar. Up to 30 µm deep microstructures have been successfully fabricated using the developed processes. The average area roughness (R a ) of the etched surface was measured and results showed it is comparable to the roughness obtained using a wet etching technique. Additionally, near-vertical sidewalls (with a taper angle up to 85°) have been obtained for the etched microstructures. The processes developed here can be applied to any application requiring fabrication of deep microstructures in fused silica with near-vertical sidewalls. To our knowledge, this is the first note on deep RIE of fused silica using a single-coated KMPR® 1025 masking layer and a non-ICP-based reactive ion etcher. (technical note)

  10. 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.

  11. Ions in solution basic principles of chemical interactions

    CERN Document Server

    Burgess, J

    1999-01-01

    This outline of the principles and chemical interactions in inorganic solution chemistry delivers a course module in an area of considerable complexity. Problems with solutions and tutorial hints to test comprehension have been added as a feature to check readers' understanding and assist self-study. Exercises and projects are also provided to help readers deepen and extend their knowledge and understanding. Inorganic solution chemistry is treated thoroughly Emphasis is placed upon NMR, UV-VIS, IR Raman spectroscopy, X-ray diffraction, and such topics as acid-base behaviour, stability constants and kinetics.

  12. Chemical reactivity of {alpha}-isosaccharinic acid in heterogeneous alkaline systems

    Energy Technology Data Exchange (ETDEWEB)

    Glaus, M. A.; Loon, L. R. Van

    2009-05-15

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, {alpha}- isosaccharinic acid ({alpha}-ISA) is the strongest complexant. The prediction of the equilibrium concentration of {alpha}-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of {alpha}-ISA in heterogeneous alkaline model systems containing either Ca(OH){sub 2} or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of {alpha}-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 {sup o}C or 90 {sup o}C, and under anaerobic atmospheres obtained by various methods. It was found that {alpha}-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than {alpha}-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was {approx} 50 % of the amount of {alpha}-ISA reacted. Sorption of {alpha}-ISA to Ca(OH){sub 2} contributed only to a minor extent to the loss of {alpha}-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of {alpha}-ISA. Under aerobic conditions {alpha}-ISA was

  13. Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

    International Nuclear Information System (INIS)

    Glaus, M. A.; Loon, L. R. Van

    2008-11-01

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α-isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, either at 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

  14. Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

    International Nuclear Information System (INIS)

    Glaus, M. A.; Loon, L. R. Van

    2009-05-01

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α- isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼ 50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

  15. Biosensor and chemical sensor probes for calcium and other metal ions

    Science.gov (United States)

    Vo-Dinh, Tuan; Viallet, Pierre

    1996-01-01

    The present invention relates to chemical sensor and biosensor probes for measuring low concentration of metals and metal ions in complex samples such as biological fluids, living cells, and environmental samples. More particularly the present invention relates to a gel-based Indo-1 and Fura-2 chemical sensor probes for the measurement of low concentrations of calcium, cadmium, magnesium and the like. Also disclosed is a detector device using the sensors of the present invention.

  16. Heterogeneously catalyzed reactive extraction for biomass valorization into chemicals and fuels

    NARCIS (Netherlands)

    Ordomskiy, V.; Khodakov, A.Y.; Nijhuis, T.A.; Schouten, J.C.

    2015-01-01

    This paper focuses on the heterogeneously catalyzed reactive extraction and separation in reaction steps in organic and aqueous phases during the transformation of biomass derived products. Two approaches are demonstrated for decomposing and preserving routes for biomass transformation into valuable

  17. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns.

    Science.gov (United States)

    Hartwig, Jan; Metternich, Jan B; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V

    2014-06-14

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  18. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns

    OpenAIRE

    Hartwig, Jan; Metternich, Jan B.; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V.

    2014-01-01

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  19. Chemical Bonding States of TiC Films before and after Hydrogen Ion Irradiation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    TiC films deposited by rf magnetron sputtering followed by Ar+ ion bombardment were irradiated with a hydrogen ion beam. X-ray photoelectron spectroscopy (XPS) was used for characterization of the chemical bonding states of C and Ti elements of the TiC films before and after hydrogen ion irradiation, in order to understand the effect of hydrogen ion irradiation on the films and to study the mechanism of hydrogen resistance of TiC films. Conclusions can be drawn that ion bombardment at moderate energy can cause preferential physical sputtering of carbon atoms from the surface of low atomic number (Z) material. This means that ion beam bombardment leads to the formation of a non-stoichiometric composition of TiC on the surface.TiC films prepared by ion beam mixing have the more excellent characteristic of hydrogen resistance. One important cause, in addition to TiC itself, is that there are many vacant sites in TiC created by ion beam mixing.These defects can easily trap hydrogen and effectively enhance the effect of hydrogen resistance.

  20. Modeling of Sheath Ion-Molecule Reactions in Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes

    Science.gov (United States)

    Hash, David B.; Govindan, T. R.; Meyyappan, M.

    2004-01-01

    In many plasma simulations, ion-molecule reactions are modeled using ion energy independent reaction rate coefficients that are taken from low temperature selected-ion flow tube experiments. Only exothermic or nearly thermoneutral reactions are considered. This is appropriate for plasma applications such as high-density plasma sources in which sheaths are collisionless and ion temperatures 111 the bulk p!asma do not deviate significantly from the gas temperature. However, for applications at high pressure and large sheath voltages, this assumption does not hold as the sheaths are collisional and ions gain significant energy in the sheaths from Joule heating. Ion temperatures and thus reaction rates vary significantly across the discharge, and endothermic reactions become important in the sheaths. One such application is plasma enhanced chemical vapor deposition of carbon nanotubes in which dc discharges are struck at pressures between 1-20 Torr with applied voltages in the range of 500-700 V. The present work investigates The importance of the inclusion of ion energy dependent ion-molecule reaction rates and the role of collision induced dissociation in generating radicals from the feedstock used in carbon nanotube growth.

  1. Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions.

    Science.gov (United States)

    Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

    2017-07-01

    Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO 3 ) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO 3 -nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO 3 ) was produced in the flame. The HNO 3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO 3 showed the strongest affinity to histidine and formed (M histidine -H+HNO 3 ) - complex ions, whereas some amino acids did not react with HNO 3 at all. Reactions between HNO 3 and histidine residues in AI and AII resulted in the formation of dominant [M AI -H+(HNO 3 )] - and [M AII -H+(HNO 3 )] - ions. Results from analyses of AAs and insulin indicated that HNO 3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO 3 ) n ] 3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins. Graphical Abstract ᅟ.

  2. Chemical characterization of microparticles by laser ablation in an ion trap mass spectrometer

    International Nuclear Information System (INIS)

    Dale, J.M.; Whitten, W.B.; Ramsey, J.M.

    1991-01-01

    We are developing a new technique for the chemical characterization of microparticles based upon the use of electrodynamic traps. The electrodynamic trap has achieved widespread use in the mass spectrometry community in the form of the ion trap mass spectrometer or quadrupole ion trap. Small macroscopic particles can be confined or levitated within the electrode structure of a three-dimensional quadrupole electrodynamic trap in the same way as fundamental charges or molecular ions by using a combination of ac and dc potentials. Our concept is to use the same electrode structure to perform both microparticle levitation and ion trapping/mass analysis. The microparticle will first be trapped and spatially stabilized within the trap for characterization by optical probes, i.e., absorption, fluorescence, or Raman spectroscopy. After the particle has been optically characterized, it is further characterized using mass spectrometry. Ions are generated from the particle surface using laser ablation or desorption. The characteristics of the applied voltages are changed to trap the ions formed by the laser with the ions subsequently mass analyzed. The work described in this paper focuses on the ability to perform laser desorption experiments on microparticles contained within the ion trap

  3. Thermal and chemical stabilities of some synthesized inorganic ion exchange materials

    International Nuclear Information System (INIS)

    EI-Naggar, I.M.; Abou-Mesalam, M.M.; El-Shorbagy, M.M.; Shady, S.A.

    2006-01-01

    Chromium and cerium titanate as inorganic ion exchange materials were synthesized by the reaction of potassium chromate or ammonium eerie nitrate with titanium tetrachloride with molar ratio equal unity. The crystal system of both chromium and cerium titanates were determined and set to be monoclinic and orthorhombic system's, respectively. The chemical composition of both chromium and cerium titanates was determined by X-ray fluorescence technique and based on the data obtained with other different techniques. A molecular formula for chromium and cerium titanates as Cr 2 Ti 12 O 27 . 13H 2 O and Ce 2 Ti 3 O 10 . 7.46H 2 O, respectively, was proposed. Thermal stabilities of both ion exchangers were investigated at different heating temperatures. Also the stability of chromium and cerium titanates for chemical attack was studied in different media. The data obtained showed high thermal and chemical stabilities of chromium and cerium titanate ion exchangers compared with the same group of ion exchange materials. The ion exchange capacities of chromium and cerium titanates at different heating temperature were also investigated

  4. Thermal and chemical stabilities of some synthesized inorganic ion exchange materials

    International Nuclear Information System (INIS)

    El-Naggar, I.M.; Abou-Mesalam, M. M.; El-Shorbagy, M.M.; Shady, S.A.

    2005-01-01

    Chromium and cerium titanate as inorganic ion exchange materials were synthesized by the reaction of potassium chromate or ammonium ceric nitrate with titanium tetrachloride with molar ratio equal unity. The crystal system of both chromium and cerium titanates were determined and set to be monoclinic and orthorhombic systems, respectively. The chemical composition of both chromium and cerium titanates were determined by X-ray fluorescence technique and based on the data obtained with other different techniques. We can proposed molecular formula for chromium and cerium titanates as Cr 2 Ti 1 2O27. 13H 2 O and Ce 2 ThO10. 7.46 H 2 O, respectively. Thermal stability of both ion exchangers was investigated at different heating temperatures. Also the stability of chromium and cerium titanates for chemical attack was studied in different media. The data obtained showed high thermal and chemical stabilities of chromium and cerium titanate ion exchangers compared to the same group of ion exchange materials. The ion exchange capacities of chromium and cerium titanates at different heating temperature were investigated

  5. Chemical exchange between UF6 and UF6- ion in anhydrous hydrofluoric acid

    International Nuclear Information System (INIS)

    Chatelet, J.; Luce, M.; Plurien, P.; Rigny, P.

    1975-01-01

    The chemical exchange between UF 6 and the UF 6 - ion is of potential interest for the separation of U isotopes. In this paper, results concerning the value of the separation factor and the kinetics of the homogeneous exchange are given [fr

  6. Electro-Analytical Study of Material Interfaces Relevant for Chemical Mechanical Planarization and Lithium Ion Batteries

    Science.gov (United States)

    Turk, Michael C.

    This dissertation work involves two areas of experimental research, focusing specifically on the applications of electro-analytical techniques for interfacial material characterization. The first area of the work is centered on the evaluation and characterization of material components used for chemical mechanical planarization (CMP) in the fabrication of semiconductor devices. This part also represents the bulk of the projects undertaken for the present dissertation. The other area of research included here involves exploratory electrochemical studies of certain electrolyte and electrode materials for applications in the development of advanced lithium ion secondary batteries. The common element between the two areas of investigation is the technical approach that combines a broad variety of electro-analytical characterization techniques to examine application specific functions of the associated materials and devices. The CMP related projects concentrate on designing and evaluating materials for CMP slurries that would be useful in the processing of copper interconnects for the sub-22 nm technology node. Specifically, ruthenium and cobalt are nontraditional barrier materials currently considered for the new interconnects. The CMP schemes used to process the structures based on these metals involve complex surface chemistries of Ru, Co and Cu (used for wiring lines). The strict requirement of defect-control while maintaining material removal by precisely regulated tribo-corrosion complicates the designs of the CMP slurries needed to process these systems. Since Ru is electrochemically more noble than Cu, the surface regions of Cu assembled in contact with Ru tend to generate defects due to galvanic corrosion in the CMP environment. At the same time, Co is strongly reactive in the typical slurry environment and is prone to developing galvanic corrosion induced by Cu. The present work explores a selected class of alkaline slurry formulations aimed at reducing these

  7. 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.

  8. Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

    Science.gov (United States)

    Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

    2014-01-28

    Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

  9. Chemical characterization of microparticles by laser ablation in an ion trap mass spectrometer

    International Nuclear Information System (INIS)

    Dale, J.M.; Whitten, W.B.; Ramsey, J.M.

    1991-01-01

    We are developing a new technique for the chemical characterization of microparticles based upon the use of electrodynamic traps. The electrodynamic trap has achieved widespread use in the mass spectrometry community in the form of the ion trap mass spectrometer or quadrupole ion trap. Small macroscopic particles can be confined or leviated within the electrode structure of a three-dimensional quadrupole electrodynamic trap in the same way as fundamental charges or molecular ions by using a combination of ac and dc potentials. Our concept is to use the same electrode structure to perform both microparticle levitation and ion trapping/mass analysis. The microparticle will first be trapped and spatially stabilized within the trap for characterization by optical probes, i.e., absorption, fluorescence, or Raman spectroscopy. After the particle has been optically characterized, it is further characterized using mass spectrometry. Ions are generated from the particle surface using laser ablation or desorption. The characteristics of the applied voltages are changed to trap the ions formed by the laser with the ions subsequently mass analyzed. The work described in this paper focuses on the ability to perform laser desorption experiments on microparticles contained within the ion trap. Laser desorption has previously been demonstrated in ion trap devices by applying the sample to a probe which is inserted so as to place the sample at the surface of the ring electrode. Our technique requires the placement of a microparticle in the center of the trap. Our initial experiments have been performed on falling microparticles rather than levitated particles to eliminate voltage switching requirements when changing from particle to ion trapping modes

  10. 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.

  11. 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.

  12. 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

  13. Reactive ion etching of tellurite and chalcogenide waveguides using hydrogen, methane, and argon

    International Nuclear Information System (INIS)

    Vu, K. T.; Madden, S. J.

    2011-01-01

    The authors report in detail on the reactive plasma etching properties of tellurium and demonstrate a high quality etching process using hydrogen, methane, and argon. Very low loss planar ridge waveguides are demonstrated. Optical losses in tellurium dioxide waveguides below 0.1 dB/cm in most of the near infrared region of the electromagnetic spectrum and at 1550 nm have been achieved--the lowest ever reported by more than an order of magnitude and clearly suitable for planar integrated devices. The etch process is also shown to be suitable for chalcogenide glasses which may be of importance in applications such as phase change memory devices and nonlinear integrated optics.

  14. 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)

  15. Stresses and Temperature Stability of Dense Wavelength Division Multiplexing Filters Prepared by Reactive Ion-Assisted E-Gun Evaporation

    Science.gov (United States)

    Wei, Chao-Tsang; Shieh, Han-Ping D.

    2005-10-01

    In this paper, we report the in situ measurement of the temperature stability of narrow-band-pass filters on different types of substrate, for dense wavelength division multiplexing (DWDM) filters in optical-fiber transmission systems. The DWDM filters were designed as all-dielectric Fabry-Perot filters and fabricated by reactive ion-assisted deposition. Ta2O5 and SiO2 were used as high- and low-refractive-index layers, respectively, for constructing the DWDM filters. The accuracy and stability of the coating process were evaluated for fabricating the DWDM filters for the temperature stability of the center wavelength. The center wavelength shift was determined to be greatly dependent on the coefficient of thermal expansion of the substrate on which the filter is deposited.

  16. Fabrication of Super-Hydrophobic Microchannels via Strain-Recovery Deformations of Polystyrene and Oxygen Reactive Ion Etch.

    Science.gov (United States)

    Chakraborty, Anirban; Xiang, Mingming; Luo, Cheng

    2013-08-19

    In this article, we report a simple approach to generate micropillars (whose top portions are covered by sub-micron wrinkles) on the inner surfaces of polystyrene (PS) microchannels, as well as on the top surface of the PS substrate, based on strain-recovery deformations of the PS and oxygen reactive ion etch (ORIE). Using this approach, two types of micropillar-covered microchannels are fabricated. Their widths range from 118 μm to 132 μm, depths vary from 40 μm to 44 μm, and the inclined angles of their sidewalls are from 53° to 64°. The micropillars enable these microchannels to have super-hydrophobic properties. The contact angles observed on the channel-structured surfaces are above 162°, and the tilt angles to make water drops roll off from these channel-structured substrates can be as small as 1°.

  17. Fabrication of Super-Hydrophobic Microchannels via Strain-Recovery Deformations of Polystyrene and Oxygen Reactive Ion Etch

    Directory of Open Access Journals (Sweden)

    Anirban Chakraborty

    2013-08-01

    Full Text Available In this article, we report a simple approach to generate micropillars (whose top portions are covered by sub-micron wrinkles on the inner surfaces of polystyrene (PS microchannels, as well as on the top surface of the PS substrate, based on strain-recovery deformations of the PS and oxygen reactive ion etch (ORIE. Using this approach, two types of micropillar-covered microchannels are fabricated. Their widths range from 118 μm to 132 μm, depths vary from 40 μm to 44 μm, and the inclined angles of their sidewalls are from 53° to 64°. The micropillars enable these microchannels to have super-hydrophobic properties. The contact angles observed on the channel-structured surfaces are above 162°, and the tilt angles to make water drops roll off from these channel-structured substrates can be as small as 1°.

  18. Wafer Surface Charge Reversal as a Method of Simplifying Nanosphere Lithography for Reactive Ion Etch Texturing of Solar Cells

    Directory of Open Access Journals (Sweden)

    Daniel Inns

    2007-01-01

    Full Text Available A simplified nanosphere lithography process has been developed which allows fast and low-waste maskings of Si surfaces for subsequent reactive ion etching (RIE texturing. Initially, a positive surface charge is applied to a wafer surface by dipping in a solution of aluminum nitrate. Dipping the positive-coated wafer into a solution of negatively charged silica beads (nanospheres results in the spheres becoming electrostatically attracted to the wafer surface. These nanospheres form an etch mask for RIE. After RIE texturing, the reflection of the surface is reduced as effectively as any other nanosphere lithography method, while this batch process used for masking is much faster, making it more industrially relevant.

  19. Temperature dependence of InN film deposition by an RF plasma-assisted reactive ion beam sputtering deposition technique

    International Nuclear Information System (INIS)

    Shinoda, Hiroyuki; Mutsukura, Nobuki

    2005-01-01

    Indium nitride (InN) films were deposited on Si(100) substrates using a radiofrequency (RF) plasma-assisted reactive ion beam sputtering deposition technique at various substrate temperatures. The X-ray diffraction patterns of the InN films suggest that the InN films deposited at substrate temperatures up to 370 deg C were cubic crystalline InN; and at 500 deg C, the InN film was hexagonal crystalline InN. In a scanning electron microscope image of the InN film surface, facets of cubic single-crystalline InN grains were clearly observed on the InN film deposited at 370 deg C. The inclusion of metallic indium appeared on the InN film deposited at 500 deg C

  20. Optimizing shape uniformity and increasing structure heights of deep reactive ion etched silicon x-ray lenses

    DEFF Research Database (Denmark)

    Stöhr, Frederik; Wright, Jonathan; Simons, Hugh

    2015-01-01

    Line-focusing compound silicon x-ray lenses with structure heights exceeding 300 μm were fabricated using deep reactive ion etching. To ensure profile uniformity over the full height, a new strategy was developed in which the perimeter of the structures was defined by trenches of constant width....... The remaining sacrificial material inside the lens cavities was removed by etching through the silicon wafer. Since the wafers become fragile after through-etching, they were then adhesively bonded to a carrier wafer. Individual chips were separated using laser micro machining and the 3D shape of fabricated...... analysis, where a slight bowing of the lens sidewalls and an insufficiently uniform apex region are identified as resolution-limiting factors. Despite these, the proposed fabrication route proved a viable approach for producing x-ray lenses with large structure heights and provides the means to improve...

  1. Generation of positive and negative oxygen ions in magnetron discharge during reactive sputtering of alumina

    Czech Academy of Sciences Publication Activity Database

    Pokorný, Petr; Bulíř, Jiří; Lančok, Ján; Musil, Jindřich; Novotný, Michal

    2010-01-01

    Roč. 7, č. 11 (2010), s. 910-914 ISSN 1612-8850 R&D Projects: GA AV ČR IAA100100718; GA AV ČR KAN400100653; GA ČR GP202/09/P324 Institutional research plan: CEZ:AV0Z10100522 Keywords : aluminium oxide * ion-energy distribution function * magnetron * mass spectrometry * pulsed discharges Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.643, year: 2010

  2. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  3. Ion transport by gating voltage to nanopores produced via metal-assisted chemical etching method

    Science.gov (United States)

    Van Toan, Nguyen; Inomata, Naoki; Toda, Masaya; Ono, Takahito

    2018-05-01

    In this work, we report a simple and low-cost way to create nanopores that can be employed for various applications in nanofluidics. Nano sized Ag particles in the range from 1 to 20 nm are formed on a silicon substrate with a de-wetting method. Then the silicon nanopores with an approximate 15 nm average diameter and 200 μm height are successfully produced by the metal-assisted chemical etching method. In addition, electrically driven ion transport in the nanopores is demonstrated for nanofluidic applications. Ion transport through the nanopores is observed and could be controlled by an application of a gating voltage to the nanopores.

  4. Chemical or electrochemical techniques, followed by ion exchange, for recycle of textile dye wastewater.

    Science.gov (United States)

    Raghu, S; Ahmed Basha, C

    2007-10-22

    This paper examines the use of chemical or electrocoagulation treatment process followed by ion-exchange process of the textile dye effluent. The dye effluent was treated using polymeric coagulant (cationic dye-fixing agent) or electrocoagulation (iron and aluminum electrode) process under various conditions such as various current densities and effect of pH. Efficiencies of COD reduction, colour removal and power consumption were studied for each process. The chemical or electrochemical treatment are indented primarily to remove colour and COD of wastewater while ion exchange is used to further improve the removal efficiency of the colour, COD, Fe concentration, conductivity, alkalinity and total dissolved solids (TDS). From the results chemical coagulation, maximum COD reduction of about 81.3% was obtained at 300 mg/l of coagulant whereas in electrocoagulation process, maximum COD removal of about 92.31% (0.25 A/dm2) was achieved with energy consumption of about 19.29 k Wh/kg of COD and 80% (1A/dm(2)) COD removal was obtained with energy consumption of about 130.095 k Wh/kg of COD at iron and aluminum electrodes, respectively. All the experimental results, throughout the present study, have indicated that chemical or electrocoagulation treatment followed by ion-exchange methods were very effective and were capable of elevating quality of the treated wastewater effluent to the reuse standard of the textile industry.

  5. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  6. Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses.

    Science.gov (United States)

    Massera, J; Petit, L; Cardinal, T; Videau, J J; Hupa, M; Hupa, L

    2013-06-01

    In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅-10Na₂-(40-x)CaO-xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.

  7. Chemical conjugation of cowpea mosaic viruses with reactive HPMA-based polymers

    Czech Academy of Sciences Publication Activity Database

    Laga, Richard; Koňák, Čestmír; Šubr, Vladimír; Ulbrich, Karel; Suthiwangcharoen, N.; Niu, Q.; Wang, Q.

    2010-01-01

    Roč. 21, č. 12 (2010), s. 1669-1685 ISSN 0920-5063 R&D Projects: GA AV ČR KJB400500803; GA ČR GA202/09/2078; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40500505 Keywords : acylthiazolidine-2-thione reactive groups * bioconjugation * coating Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.842, year: 2010

  8. Thermogravimetric study on the influence of structural, textural and chemical properties of biomass chars on CO2 gasification reactivity

    International Nuclear Information System (INIS)

    Bouraoui, Zeineb; Jeguirim, Mejdi; Guizani, Chamseddine; Limousy, Lionel; Dupont, Capucine; Gadiou, Roger

    2015-01-01

    The present investigation aims to examine the influence of textural, structural and chemical properties of biomass chars on the CO 2 gasification rate. Various lignocellulosic biomass chars were prepared under the same conditions. Different analytical techniques were used to determine the char properties such as Scanning Electronic Microscopy, nitrogen adsorption manometry, Raman spectroscopy and X Ray Fluorescence. Gasification tests were carried out in a thermobalance under 20% CO 2 in nitrogen at 800 °C. Significant differences of the total average reactivity were observed with a factor of 2 between the prepared chars. Moreover, different behaviors of gasification rate profiles versus conversion were obtained. This difference of behavior appeared to be correlated with the biomass char properties. Hence, up to 70% of conversion, the gasification rate was shown to depend on the char external surface and the potassium content. At higher conversion ratio, a satisfactory correlation between the Catalytic Index and the average gasification rate was identified. The results highlight the importance of knowing both textural and structural properties and mineral contents of biomass chars to predict fuel reactivity during CO 2 gasification processes. Such behavior prediction is highly important in the gasifiers design for char conversion. - Highlights: • CO 2 gasification reactivity of various lignocellulosic chars were examined. • Chars properties affect strongly samples gasification behavior. • Initial gasification rate is affected by external surface, K content and D3/G ratio. • Gasification rate behavior depends on the Alkali index at high conversion

  9. The effect of FR enhancement in reactive ion beam sputtered Bi, Gd, Al-substituted iron- garnets: Bi2O3 nanocomposite films

    OpenAIRE

    Berzhansky, V.; Shaposhnikov, A.; Karavainikov, A.; Prokopov, A.; Mikhailova, T.; Lukienko, I.; Kharchenko, Yu.; Miloslavskaya, O.; Kharchenko, N.

    2012-01-01

    The effect of considerable Faraday rotation (FR) and figure of merit (Q) enhancement in Bi, Gd, Al-substituted iron garnets: Bi2O3 nano-composite films produced by separate reactive ion beam sputtered Bi:YIG and Bi2O3 films was found. It reached threefold enhancement of the FR and twofold of the Q one on GGG substrates.

  10. Determination of clebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

    Science.gov (United States)

    Robinson, P R; Jones, M D; Maddock, J

    1988-11-18

    A procedure for the analysis of clebopride in plasma using capillary gas chromatography-negative-ion chemical ionization mass spectrometry has been developed. Employing an ethoxy analogue as internal standard, the two compounds were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyryl imidazole produced volatile monoheptafluorobutyryl derivatives whose ammonia negative-ion mass spectra proved ideal for selected-ion monitoring. The recovery of clebopride from plasma at 0.536 nmol/l was found to be 85.5 +/- 0.9% (n = 3) whilst measurement down to 0.268 nmol/l was possible with a coefficient of variation of 7.9%. Plasma levels of the compound are reported in two volunteers following ingestion of 1 mg of clebopride as the malate salt.

  11. The Atmospheric Tomography Mission (ATom): Comparing the Chemical Climatology of Reactive Species and Air Parcels from Measurements and Global Models

    Science.gov (United States)

    Prather, M. J.; Flynn, C.; Wennberg, P. O.; Kim, M. J.; Ryerson, T. B.; Hanisco, T. F.; Diskin, G. S.; Daube, B. C.; Commane, R.; McKain, K.; Apel, E. C.; Blake, N. J.; Blake, D. R.; Elkins, J. W.; Hall, S.; Steenrod, S.; Strahan, S. E.; Lamarque, J. F.; Fiore, A. M.; Horowitz, L. W.; Murray, L. T.; Mao, J.; Shindell, D. T.; Wofsy, S. C.

    2017-12-01

    The NASA Atmospheric Tomography Mission (ATom) is building a photochemical climatology of the remote troposphere based on objective sampling and profiling transects over the Pacific and Atlantic Oceans. These statistics provide direct tests of chemistry-climate models. The choice of species focuses on those controlling primary reactivity (a.k.a. oxidative state) of the troposphere, specifically chemical tendencies of O3 and CH4. These key species include, inter alia, O3, CH4, CO, C2H6, other alkanes, alkenes, aromatics, NOx, HNO3, HO2NO2, PAN, other organic nitrates, H2O, HCHO, H2O2, CH3OOH. Three of the four ATom deployments are now complete, and data from the first two (ATom-1 & -2) have been released as of this talk (see espoarchive.nasa.gov/archive/browse/atom). The statistical distributions of key species are presented as 1D and 2D probability densities (PDs) and we focus here on the tropical and mid-latitude regions of the Pacific during ATom-1 (Aug) and -2 (Feb). PDs are computed from ATom observations and 6 global chemistry models over the tropospheric depth (0-12 km) and longitudinal extent of the observations. All data are weighted to achieve equal mass-weighting by latitude regimes to account for spatial sampling biases. The models are used to calculate the reactivity in each ATom air parcel. Reweighting parcels with loss of CH4 or production of O3, for example, allows us to identify which air parcels are most influential, including assessment of the importance of fine pollution layers in the most remote troposphere. Another photochemical climatology developed from ATom, and used to test models, includes the effect of clouds on photolysis rates. The PDs and reactivity-weighted PDs reveal important seasonal differences and similarities between the two campaigns and also show which species may be most important in controlling reactivities. They clearly identify some very specific failings in the modeled climatologies and help us evaluate the chemical

  12. Application of Photocured Polymer Ion Selective Membranes for Solid-State Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Natalia Abramova

    2015-06-01

    Full Text Available Application of conducting polymers with additional functional groups for a solid contact formation and photocurable membranes as sensitive elements of solid-state chemical sensors is discussed. Problems associated with application of UV-curable polymers for sensors are analyzed. A method of sensor fabrication using copolymerized conductive layer and sensitive membrane is presented and the proof of concept is confirmed by two examples of solid-contact electrodes for Ca ions and pH.

  13. Chemically Etched Silicon Nanowires as Anodes for Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    West, Hannah Elise [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-08-01

    This study focused on silicon as a high capacity replacement anode for Lithium-ion batteries. The challenge of silicon is that it expands ~270% upon lithium insertion which causes particles of silicon to fracture, causing the capacity to fade rapidly. To account for this expansion chemically etched silicon nanowires from the University of Maine were studied as anodes. They were built into electrochemical half-cells and cycled continuously to measure the capacity and capacity fade.

  14. Relativistic total energy and chemical potential of heavy atoms and positive ions

    International Nuclear Information System (INIS)

    Hill, S.H.; Grout, P.J.; March, N.H.

    1984-01-01

    The relativistic Thomas-Fermi theory, with a finite nucleus, is used to study the variation of the chemical potential μ with atomic number Z and number of electrons N (N <= Z). The difference between the total energy of positive ions and that of the corresponding neutral atom has been obtained. The scaling predictions are confirmed by numerical calculations. The first principles calculation of the relativistic Thomas-Fermi total energy of neutral atoms is also studied. (author)

  15. Effects of ion-neutral chemical reactions on dynamics of lightning-induced electric field

    International Nuclear Information System (INIS)

    Hiraki, Yasutaka

    2009-01-01

    Secondary lightning phenomena in the upper atmosphere called sprites attract interest from the viewpoint of atomic-molecular and plasma physics. Lightning-induced electric field accelerates the ionospheric electrons up to tens of electron-volts, inducing electrical breakdown as well as strong optical emissions, through electron impact ionization of molecules. A large-scale structure of sprites is constructed by collective dynamics of filamentary streamer discharges in a rarified gas, which in turn is controlled by the distribution of the background electric field. In this paper, we firstly reanalyze the relationship between quasi-static field formation and local ion chemistry with first-order perturbation techniques. Secondly, we investigate with a full ion chemical model the effects of electron attachment to oxygen molecules on its density in moderate cases of undervoltage lightning electric fields rather than the cases of intense ionization in streamers. We estimate the minimum values that are provided by the chemical balance with electron detachment from negative ions. We also investigate the recovery timescale of the electron density and find that the scale (≥1 s) is occasionally much larger than the interval of each lightning stroke (∼10 ms). We suggest that the subsequent sprite event as well as the field formation could be well affected by the ghost of the primary event. We discuss further the negative ion chemistry triggered by electron attachment in the nighttime mesosphere.

  16. Acoustic sensors for the control of liquid-solid interface evolution and chemical reactivity

    International Nuclear Information System (INIS)

    Ferrandis, J.Y.; Tingry, S.; Attal, J.; Seta, P.

    2006-01-01

    Less classical than far-field acoustic investigations of solid materials and/or solid-liquid interfaces, near-field acoustic properties of an acoustic solid wave guide (tip), thin enough at its termination to present an external diameter smaller than the excitation acoustic wave wavelength, is shown to be able to probe interface properties. As a result of that, these near-field acoustic probes can play the role of chemical sensors, if chemical modifications or chemical reactions are concerned at their surface. In that context, a chemical sensor was realized by electrochemical deposition of an electron-conducting polymer (polypyrrole-biotin) on a metal tip, followed by enzyme attachment by molecular recognition process involving the biotin-avidin-specific interaction. Results from near-field acoustic showed that the enzyme modification of the polymer layer can be detected by this new acoustic sensor

  17. Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

    Science.gov (United States)

    Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

    2016-02-18

    Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

  18. Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

    Science.gov (United States)

    Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

    2014-04-01

    Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

  19. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  20. Establishment and intra-/inter-laboratory validation of a standard protocol of reactive oxygen species assay for chemical photosafety evaluation.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Matsuoka, Naoko; Nakamura, Kazuichi; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Seto, Yoshiki; Kato, Masashi; Yamada, Shizuo; Ohno, Yasuo; Kojima, Hajime

    2013-11-01

    A reactive oxygen species (ROS) assay was previously developed for photosafety evaluation of pharmaceuticals, and the present multi-center study aimed to establish and validate a standard protocol for ROS assay. In three participating laboratories, two standards and 42 coded chemicals, including 23 phototoxins and 19 nonphototoxic drugs/chemicals, were assessed by the ROS assay according to the standardized protocol. Most phototoxins tended to generate singlet oxygen and/or superoxide under UV-vis exposure, but nonphototoxic chemicals were less photoreactive. In the ROS assay on quinine (200 µm), a typical phototoxic drug, the intra- and inter-day precisions (coefficient of variation; CV) were found to be 1.5-7.4% and 1.7-9.3%, respectively. The inter-laboratory CV for quinine averaged 15.4% for singlet oxygen and 17.0% for superoxide. The ROS assay on 42 coded chemicals (200 µm) provided no false negative predictions upon previously defined criteria as compared with the in vitro/in vivo phototoxicity, although several false positives appeared. Outcomes from the validation study were indicative of satisfactory transferability, intra- and inter-laboratory variability, and predictive capacity of the ROS assay. Copyright © 2012 John Wiley & Sons, Ltd.

  1. Modeling the transport of chemical warfare agents and simulants in polymeric substrates for reactive decontamination

    Science.gov (United States)

    Pearl, Thomas; Mantooth, Brent; Varady, Mark; Willis, Matthew

    2014-03-01

    Chemical warfare agent simulants are often used for environmental testing in place of highly toxic agents. This work sets the foundation for modeling decontamination of absorbing polymeric materials with the focus on determining relationships between agents and simulants. The correlations of agents to simulants must consider the three way interactions in the chemical-material-decontaminant system where transport and reaction occur in polymer materials. To this end, diffusion modeling of the subsurface transport of simulants and live chemical warfare agents was conducted for various polymer systems (e.g., paint coatings) with and without reaction pathways with applied decontamination. The models utilized 1D and 2D finite difference diffusion and reaction models to simulate absorption and reaction in the polymers, and subsequent flux of the chemicals out of the polymers. Experimental data including vapor flux measurements and dynamic contact angle measurements were used to determine model input parameters. Through modeling, an understanding of the relationship of simulant to live chemical warfare agent was established, focusing on vapor emission of agents and simulants from materials.

  2. Topological analysis (BCP) of vibrational spectroscopic studies, docking, RDG, DSSC, Fukui functions and chemical reactivity of 2-methylphenylacetic acid

    Science.gov (United States)

    Kavimani, M.; Balachandran, V.; Narayana, B.; Vanasundari, K.; Revathi, B.

    2018-02-01

    Experimental FT-IR and FT-Raman spectra of 2-methylphenylacetic acid (MPA) were recorded and theoretical values are also analyzed. The non-linear optical (NLO) properties were evaluated by determination of first (5.5053 × 10- 30 e.s.u.) and second hyper-polarizabilities (7.6833 × 10- 36 e.s.u.) of the title compound. The Multiwfn package is used to find the weak non-covalent interaction (Van der Wall interaction) and strong repulsion (steric effect) of the molecule and examined by reduced density gradient. The molecular electrostatic potential (MEP) analysis used to find the most reactive sites for the electrophilic and nucleophilic attack. The chemical activity (electronegativity, hardness, chemical softness and chemical potential) of the title compound was predicted with the help of HOMO-LUMO energy values. The natural bond orbital (NBO) has been analyzed the stability of the molecule arising from the hyper-conjugative interaction. DSSCs were discussed in structural modifications that improve the electron injection efficiency of the title compound (MPA). The Fukui functions are calculated in order to get information associated with the local reactivity properties of the title compound. The binding sites of the two receptors were reported by molecular docking field and active site bond distance is same 1.9 Å. The inhibitor of the title compound forms a stable complex with 1QYV and 2H1K proteins at the binding energies are - 5.38 and - 5.85 (Δ G in kcal/mol).

  3. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    Science.gov (United States)

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-06

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

  4. Chemical potentials of π- and π+ in heavy-ion collisions

    International Nuclear Information System (INIS)

    Gorenstejn, M.I.; Shin Nan Yang.

    1991-01-01

    We consider a chemical nonequilibrium model to describe the pion production in Ar+KCl and La+La collisions at initial energies E lab /A=(0.5-1.8) GeV/nucl. The excess of low energy π - is interpreted as the manifestation of positive chemical potential of π - at the thermal freeze out. We find that in collisions between nuclei with large atomic numbers the chemical potential of π + is smaller than that of π - . This leads to the prediction of a much less excess of low-energy π + , than as measured in the π - case, in heavy-ion collisions at bombarding energies in the region of 1 GeV/nucl. 17 refs.; 2 figs. (author)

  5. Different Reactive Oxygen Species Lead to Distinct Changes of Cellular Metal Ions in the Eukaryotic Model Organism Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Peter J. Rogers

    2011-11-01

    Full Text Available Elemental uptake and export of the cell are tightly regulated thereby maintaining the ionomic homeostasis. This equilibrium can be disrupted upon exposure to exogenous reactive oxygen species (ROS, leading to reduction or elevation of the intracellular metal ions. In this study, the ionomic composition in the eukaryotic model organism Saccharomyces cerevisiae was profiled using the inductively-coupled plasma optical emission spectrometer (ICP-OES following the treatment with individual ROS, including hydrogen peroxide, cumen hydroperoxide, linoleic acid hydroperoxide (LAH, the superoxide-generating agent menadione, the thiol-oxidising agent diamide [diazine-dicarboxylic acid-bis(dimethylamide], dimedone and peroxynitrite. The findings demonstrated that different ROS resulted in distinct changes in cellular metal ions. Aluminium (Al3+ level rose up to 50-fold after the diamide treatment. Cellular potassium (K+ in LAH-treated cells was 26-fold less compared to the non-treated controls. The diamide-induced Al3+ accumulation was further validated by the enhanced Al3+ uptake along the time course and diamide doses. Pre-incubation of yeast with individual elements including iron, copper, manganese and magnesium failed to block diamide-induced Al3+ uptake, suggesting Al3+-specific transporters could be involved in Al3+ uptake. Furthermore, LAH-induced potassium depletion was validated by a rescue experiment in which addition of potassium increased yeast growth in LAH-containing media by 26% compared to LAH alone. Taken together, the data, for the first time, demonstrated the linkage between ionomic profiles and individual oxidative conditions.

  6. Typical parameters of the plasma chemical similarity in non-isothermal reactive plasmas

    International Nuclear Information System (INIS)

    Gundermann, S.; Jacobs, H.; Miethke, F.; Rutsher, A.; Wagner, H.E.

    1996-01-01

    The substance of physical similarity principles is contained in parameters which govern the comparison of different realizations of a model device. Because similarity parameters for non-isothermal plasma chemical reactors are unknown to a great extent, an analysis of relevant equations is given together with some experimental results. Modelling of the reactor and experimental results for the ozone synthesis are presented

  7. Electrochemical and Quantum Chemical Study of Reactivity of Orthophthalaldehyde with Aliphatic Primary Amines

    Czech Academy of Sciences Publication Activity Database

    Donkeng Dazie, Joel; Liška, Alan; Ludvík, Jiří

    2016-01-01

    Roč. 163, č. 9 (2016), G127-G132 ISSN 0013-4651 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : electrochemistry * quantum chemical study * amines Subject RIV: CG - Electrochemistry Impact factor: 3.259, year: 2016

  8. Development of a QSAR for worst case estimates of acute toxicity of chemically reactive compounds

    NARCIS (Netherlands)

    Freidig, A.P.; Dekkers, S.; Verwei, M.; Zvinavashe, E.; Bessems, J.G.M.; Sandt, van de J.J.M.

    2007-01-01

    Future EU legislations enforce a fast hazard and risk assessment of thousands of existing chemicals. If conducted by means of present data requirements, this assessment will use a huge number of test animals and will be neither cost nor time effective. The purpose of the current research was to

  9. Surface area and chemical reactivity characteristics of uranium metal corrosion products.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-02-17

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m{sup 2}/g. The reactivity of the products in Ar-9%O{sub 2} and Ar-20%O{sub 2} were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal.

  10. Quantum mechanical reactive scattering theory for simple chemical reactions: Recent developments in methodology and applications

    International Nuclear Information System (INIS)

    Miller, W.H.

    1989-08-01

    It has recently been discovered that the S-matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has made a major contribution to heavy particle reactive (and also to electron-atom/molecule) scattering which involve non-local (i.e., exchange) interactions that prevent solution of the coupled channel equations by propagation methods. This paper reviews the methodology briefly and presents a sample of integral and differential cross sections that have been obtained for the H + H 2 → H 2 +H and D + H 2 → HD + H reactions in the high energy region (up to 1.2 eV translational energy) relevant to resonance structures reported in recent experiments. 35 refs., 11 figs

  11. Surface area and chemical reactivity characteristics of uranium metal corrosion products

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m 2 /g. The reactivity of the products in Ar-9%O 2 and Ar-20%O 2 were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal

  12. Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k

    Science.gov (United States)

    Mcgee, H. A., Jr.

    1973-01-01

    The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.

  13. Attempts to identify a control system for chemical reactivity in the living state using virtual energy.

    Science.gov (United States)

    Reid, B L; Bourke, C

    2001-07-01

    This thesis explores the activation of chemicals in metabolic systems from the viewpoint that this activation is under the control of elements of the space-sea in which the chemicals are immersed. Themselves inert, the chemicals are theorised to exploit a force or action issuing from space (fluctuation) and characterized by the homogeneity (termed symmetry) of this medium. The fluctuation is heterogenized upon collision with matter from the intervention of well recognized fields of gravity and electromagnetism at the instant of its issue to form the near field of radiation. Fractions of original space waves and of their intrinsic spin are produced resulting in the activation of the orbitals (valency) in the chemical itself. The thesis continues: the disturbed fluctuation must return to space, obliging in turn, a prior return to the homogeneous state requiring special restorative wave rearrangements known as resonance. The success of the restorative resonance is signalled by a singularity of the fluctuation now propelled to infinity (space), and the contingent chemical reactions thereby terminated. Compromise to this return can occur from many causes and, in its presence, activation of the orbitals continues. They now effectively constitute autonomous reactions alienated from the system as a whole. The thesis is supported from evidence from diverse fields such as space theory, history of quantum field theory in attempts to derive its meaning, dielectrics and the near field of electromagnetic radiation, electron-space interactions at the Fermi surface during phase transitions and evolution of equilibrium conditions in resonance phenomena. The utility of the hypothesis rests on recognition of the resonance condition at various points in the system sufficiently macroscopic as to be available clinically as an abrupt interface between physiology and pathology. Copyright 2001 Harcourt Publishers Ltd.

  14. Role of Extracellular Polymeric Substances in the Surface Chemical Reactivity of Hymenobacter aerophilus, a Psychrotolerant Bacterium▿

    Science.gov (United States)

    Baker, M. G.; Lalonde, S. V.; Konhauser, K. O.; Foght, J. M.

    2010-01-01

    Bacterial surface layers, such as extracellular polymeric substances (EPS), are known to play an important role in metal sorption and biomineralization; however, there have been very few studies investigating how environmentally induced changes in EPS production affect the cell's surface chemistry and reactivity. Acid-base titrations, cadmium adsorption assays, and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the surface reactivities of Hymenobacter aerophilus cells with intact EPS (WC) or stripped of EPS (SC) and purified EPS alone. Linear programming modeling of titration data showed SC to possess functional groups corresponding to phosphoryl (pKa ∼6.5), phosphoryl/amine (pKa ∼7.9), and amine/hydroxyl (pKa ∼9.9). EPS and WC both possess carboxyl groups (pKa ∼5.1 to 5.8) in addition to phosphoryl and amine groups. FT-IR confirmed the presence of polysaccharides and protein in purified EPS that can account for the additional carboxyl groups. An increased ligand density was observed for WC relative to that for SC, leading to an increase in the amount of Cd adsorbed (0.53 to 1.73 mmol/liter per g [dry weight] and 0.53 to 0.59 mmol/liter per g [dry weight], respectively). Overall, the presence of EPS corresponds to an increase in the number and type of functional groups on the surface of H. aerophilus that is reflected by increased metal adsorption relative to that for EPS-free cells. PMID:19915039

  15. Role of extracellular polymeric substances in the surface chemical reactivity of Hymenobacter aerophilus, a psychrotolerant bacterium.

    Science.gov (United States)

    Baker, M G; Lalonde, S V; Konhauser, K O; Foght, J M

    2010-01-01

    Bacterial surface layers, such as extracellular polymeric substances (EPS), are known to play an important role in metal sorption and biomineralization; however, there have been very few studies investigating how environmentally induced changes in EPS production affect the cell's surface chemistry and reactivity. Acid-base titrations, cadmium adsorption assays, and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the surface reactivities of Hymenobacter aerophilus cells with intact EPS (WC) or stripped of EPS (SC) and purified EPS alone. Linear programming modeling of titration data showed SC to possess functional groups corresponding to phosphoryl (pKa approximately 6.5), phosphoryl/amine (pKa approximately 7.9), and amine/hydroxyl (pKa approximately 9.9). EPS and WC both possess carboxyl groups (pKa approximately 5.1 to 5.8) in addition to phosphoryl and amine groups. FT-IR confirmed the presence of polysaccharides and protein in purified EPS that can account for the additional carboxyl groups. An increased ligand density was observed for WC relative to that for SC, leading to an increase in the amount of Cd adsorbed (0.53 to 1.73 mmol/liter per g [dry weight] and 0.53 to 0.59 mmol/liter per g [dry weight], respectively). Overall, the presence of EPS corresponds to an increase in the number and type of functional groups on the surface of H. aerophilus that is reflected by increased metal adsorption relative to that for EPS-free cells.

  16. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    Science.gov (United States)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

  17. 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.

  18. Ion-irradiation induced chemical ordering of FePt and FePtAu nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Seetala, Naidu V. [Department of Physics, Grambling State University, RWE Jones Drive, Carver Hall 81, Grambling, LA 71245 (United States)]. E-mail: naidusv@gram.edu; Harrell, J.W. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Lawson, Jeremy [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Nikles, David E. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Williams, John R. [Department of Physics, Auburn University, Auburn, AL 36849 (United States); Isaacs-Smith, Tamara [Department of Physics, Auburn University, Auburn, AL 36849 (United States)

    2005-12-15

    We have studied the effect of ion-beam irradiation on reducing the ordering temperature of FePt and FePtAu nanoparticles. FePt and FePt(Au14%) 4 nm particles dispersed on a Si-substrate were irradiated by 300 keV Al-ions with a dose of 1 x 10{sup 16} ions/cm{sup 2} at 43 {sup o}C using a water-cooled flange in order to minimize the vacancy migration and voids formation within the collision cascades. Partial chemical ordering has been observed in as-irradiated particles with coercivity of 60-130 Oe. Post-irradiation annealing at 220 {sup o}C enhanced chemical ordering in FePt nanoparticles with coercivity of 3500 Oe, magnetic anisotropy of 1.5 x 10{sup 7} erg/cc, and thermal stability factor of 130. A much higher 375 {sup o}C post-irradiation annealing was required in FePtAu, presumably because Au atoms were trapped at Fe/Pt lattice sites at lower temperatures. As the annealing temperature increased, anomalous features in the magnetization reversal curves were observed that disappeared at higher annealing temperatures.

  19. Origin of Enhanced Reactivity of a Microsolvated Nucleophile in Ion Pair SN2 Reactions: The Cases of Sodium p-Nitrophenoxide with Halomethanes in Acetone.

    Science.gov (United States)

    Li, Qiang-Gen; Xu, Ke; Ren, Yi

    2015-04-30

    In a kinetic experiment on the SN2 reaction of sodium p-nitrophenoxide with iodomethane in acetone-water mixed solvent, Humeres et al. (J. Org. Chem. 2001, 66, 1163) found that the reaction depends strongly on the medium, and the fastest rate constant was observed in pure acetone. The present work tries to explore why acetone can enhance the reactivity of the title reactions. Accordingly, we make a mechanistic study on the reactions of sodium p-nitrophenoxide with halomethanes (CH3X, X = Cl, Br, I) in acetone by using a supramolecular/continuum model at the PCM-MP2/6-311+G(d,p)//B3LYP/6-311+G(d,p) level, in which the ion pair nucleophile is microsolvated by one to three acetone molecules. We compared the reactivity of the microsolvated ion pair nucleophiles with solvent-free ion pair and anionic ones. Our results clearly reveal that the microsolvated ion pair nucleophile is favorable for the SN2 reactions; meanwhile, the origin of the enhanced reactivity induced by microsolvation of the nucleophile is discussed in terms of the geometries of transition state (TS) structures and activation strain model, suggesting that lower deformation energies and stronger interaction energies between the deformed reactants in the TS lead to the lower overall reaction barriers for the SN2 reaction of microsolvated sodium p-nitrophenoxide toward halomethanes in acetone.

  20. Surface photovoltage studies of p-type AlGaN layers after reactive-ion etching

    Science.gov (United States)

    McNamara, J. D.; Phumisithikul, K. L.; Baski, A. A.; Marini, J.; Shahedipour-Sandvik, F.; Das, S.; Reshchikov, M. A.

    2016-10-01

    The surface photovoltage (SPV) technique was used to study the surface and electrical properties of Mg-doped, p-type AlxGa1-xN (0.06 GaN:Mg thin films and from the predictions of a thermionic model for the SPV behavior. In particular, the SPV of the p-AlGaN:Mg layers exhibited slower-than-expected transients under ultraviolet illumination and delayed restoration to the initial dark value. The slow transients and delayed restorations can be attributed to a defective surface region which interferes with normal thermionic processes. The top 45 nm of the p-AlGaN:Mg layer was etched using a reactive-ion etch which caused the SPV behavior to be substantially different. From this study, it can be concluded that a defective, near-surface region is inhibiting the change in positive surface charge by allowing tunneling or hopping conductivity of holes from the bulk to the surface, or by the trapping of electrons traveling to the surface by a high concentration of defects in the near-surface region. Etching removes the defective layer and reveals a region of presumably higher quality, as evidenced by substantial changes in the SPV behavior.

  1. Probing molecules on a surface by Cs+ reactive ion scattering: identification of C2Hx (x≤4) hydrocarbons

    International Nuclear Information System (INIS)

    Kang, H.; Lee, C.W.; Hwang, C.H.; Kim, C.M.

    2003-01-01

    We studied molecular species appearing in the reactions of ethylene on a Pt(1 1 1) surface by the technique of Cs + reactive ion scattering (Cs + RIS). Dehydrogenation reaction of ethylene was examined for a surface temperature range of 100-800 K, and the RIS result verified the well-known sequence of forming di-σ-bonded ethylene (-CH 2 -CH 2 -), ethylidyne (≡C-CH 3 ), CH, and then surface carbons, as the temperature increased. In particular, the intermediate species in the conversion of ethylene to ethylidyne was closely investigated, which showed the presence of an ethylidene intermediate (≡CH-CH 3 ). In a study of H/D exchange reactions between surface C 2 D 4 and H, we successfully identified the ethylenes in which several deuterium atoms were substituted by hydrogen (C 2 D 4-x H x ,x=0-4), and quantitatively determined their relative populations. These examples demonstrate the ability of the Cs + RIS method to identify small hydrocarbons and their isotope-exchanged species on surfaces

  2. Reactive ion etching of GaSb, (Al,Ga)Sb, and InAs for novel device applications

    International Nuclear Information System (INIS)

    LaTulipe, D.C.; Frank, D.J.; Munekata, H.

    1991-01-01

    Although a variety of novel device proposals for GaSb/(Al,Ga)Sb/InAs heterostructures have been made, relatively little is known about processing these materials. The authors of this paper have studied the reactive ion etching characteristics of GaSb, (Al,Ga)Sb, and InAs in both methane/hydrogen and chlorine gas chemistries. At conditions similar to those reported elsewhere for RIE of InP and GaAs in CH 4 /H 2 , the etch rate of (Al,Ga)Sb was found to be near zero, while GaSb and InAs etched at 200 Angstrom/minute. Under conditions where the etch mechanism is primarily physical sputtering, the three compounds etch at similar rates. Etching in Cl 2 was found to yield anistropic profiles, with the etch rate of (Al,Ga)Sb increasing with Al mole fraction, while InAs remains unetched. Damage to the InAs stop layer was investigated by sheet resistance and mobility measurements. These etching techniques were used to fabricate a novel InAs- channel FET composed of these materials. Several scanning electron micrographs of etching results are shown along with preliminary electrical characteristics

  3. Investigations on diamond nanostructuring of different morphologies by the reactive-ion etching process and their potential applications.

    Science.gov (United States)

    Kunuku, Srinivasu; Sankaran, Kamatchi Jothiramalingam; Tsai, Cheng-Yen; Chang, Wen-Hao; Tai, Nyan-Hwa; Leou, Keh-Chyang; Lin, I-Nan

    2013-08-14

    We report the systematic studies on the fabrication of aligned, uniform, and highly dense diamond nanostructures from diamond films of various granular structures. Self-assembled Au nanodots are used as a mask in the self-biased reactive-ion etching (RIE) process, using an O2/CF4 process plasma. The morphology of diamond nanostructures is a close function of the initial phase composition of diamond. Cone-shaped and tip-shaped diamond nanostructures result for microcrystalline diamond (MCD) and nanocrystalline diamond (NCD) films, whereas pillarlike and grasslike diamond nanostructures are obtained for Ar-plasma-based and N2-plasma-based ultrananocrystalline diamond (UNCD) films, respectively. While the nitrogen-incorporated UNCD (N-UNCD) nanograss shows the most-superior electron-field-emission properties, the NCD nanotips exhibit the best photoluminescence properties, viz, different applications need different morphology of diamond nanostructures to optimize the respective characteristics. The optimum diamond nanostructure can be achieved by proper choice of granular structure of the initial diamond film. The etching mechanism is explained by in situ observation of optical emission spectrum of RIE plasma. The preferential etching of sp(2)-bonded carbon contained in the diamond films is the prime factor, which forms the unique diamond nanostructures from each type of diamond films. However, the excited oxygen atoms (O*) are the main etching species of diamond film.

  4. Nanostructuring of Mo/Si multilayers by means of reactive ion etching using a three-level mask

    International Nuclear Information System (INIS)

    Dreeskornfeld, L.; Haindl, G.; Kleineberg, U.; Heinzmann, U.; Shi, F.; Volland, B.; Rangelow, I.W.; Majkova, E.; Luby, S.; Kostic,; Matay, L.; Hrkut, P.; Hudek, P.; Lee, H.-Y.

    2004-01-01

    Recently, Mo/Si multilayer reflectors have been gaining industry interest as a promising choice for the next generation extreme ultraviolet mask material for printing sub 70 nm feature size devices. A reactive ion etching system with optimized hardware using CHF 3 /Ar process regime shows the capability for highly anisotropic etching of sub congruent with 400 nm feature sizes in Mo/Si test multilayers with ten periods and a bilayer thickness of 7.8 nm which were prepared by e-beam evaporation. A three-level-mask technique consisting of a top resist mask layer poly-methyl-meth-acrylate, a middle hard amorphous Si mask layer and a bottom-level polyimide layer is used to create the etch mask. The etch characteristics of the polyimide film is shown to be one of the major factors determining the success of the described multilayer etching process. The developed etching technology demonstrates superior process performance without facets, excellent uniformity and good profile control. No contamination, degeneration or defect generation in the unetched multilayer structure could be detected. This non-conventional process results in minimum deposition during the etching thus eliminating the need for a dry or wet cleaning. Sidewall angles in Mo/Si multilayers of 85 deg. , without undercut, bowing and ripples resulting in smooth sidewalls are achieved

  5. An optical MEMS accelerometer fabricated using double-sided deep reactive ion etching on silicon-on-insulator wafer

    Science.gov (United States)

    Teo, Adrian J. T.; Li, Holden; Tan, Say Hwa; Yoon, Yong-Jin

    2017-06-01

    Optical MEMS devices provide fast detection, electromagnetic resilience and high sensitivity. Using this technology, an optical gratings based accelerometer design concept was developed for seismic motion detection purposes that provides miniaturization, high manufacturability, low costs and high sensitivity. Detailed in-house fabrication procedures of a double-sided deep reactive ion etching (DRIE) on a silicon-on-insulator (SOI) wafer for a micro opto electro mechanical system (MOEMS) device are presented and discussed. Experimental results obtained show that the conceptual device successfully captured motion similar to a commercial accelerometer with an average sensitivity of 13.6 mV G-1, and a highest recorded sensitivity of 44.1 mV G-1. A noise level of 13.5 mV was detected due to experimental setup limitations. This is the first MOEMS accelerometer developed using double-sided DRIE on SOI wafer for the application of seismic motion detection, and is a breakthrough technology platform to open up options for lower cost MOEMS devices.

  6. An optical MEMS accelerometer fabricated using double-sided deep reactive ion etching on silicon-on-insulator wafer

    International Nuclear Information System (INIS)

    Teo, Adrian J T; Li, Holden; Yoon, Yong-Jin; Tan, Say Hwa

    2017-01-01

    Optical MEMS devices provide fast detection, electromagnetic resilience and high sensitivity. Using this technology, an optical gratings based accelerometer design concept was developed for seismic motion detection purposes that provides miniaturization, high manufacturability, low costs and high sensitivity. Detailed in-house fabrication procedures of a double-sided deep reactive ion etching (DRIE) on a silicon-on-insulator (SOI) wafer for a micro opto electro mechanical system (MOEMS) device are presented and discussed. Experimental results obtained show that the conceptual device successfully captured motion similar to a commercial accelerometer with an average sensitivity of 13.6 mV G −1 , and a highest recorded sensitivity of 44.1 mV G −1 . A noise level of 13.5 mV was detected due to experimental setup limitations. This is the first MOEMS accelerometer developed using double-sided DRIE on SOI wafer for the application of seismic motion detection, and is a breakthrough technology platform to open up options for lower cost MOEMS devices. (technical note)

  7. Double stratification effects in chemically reactive squeezed Sutterby fluid flow with thermal radiation and mixed convection

    Science.gov (United States)

    Ahmad, S.; Farooq, M.; Javed, M.; Anjum, Aisha

    2018-03-01

    A current analysis is carried out to study theoretically the mixed convection characteristics in squeezing flow of Sutterby fluid in squeezed channel. The constitutive equation of Sutterby model is utilized to characterize the rheology of squeezing phenomenon. Flow characteristics are explored with dual stratification. In flowing fluid which contains heat and mass transport, the first order chemical reaction and radiative heat flux affect the transport phenomenon. The systems of non-linear governing equations have been modulating which then solved by mean of convergent approach (Homotopy Analysis Method). The graphs are reported and illustrated for emerging parameters. Through graphical explanations, drag force, rate of heat and mass transport are conversed for different pertinent parameters. It is found that heat and mass transport rate decays with dominant double stratified parameters and chemical reaction parameter. The present two-dimensional examination is applicable in some of the engineering processes and industrial fluid mechanics.

  8. Quasi-equilibria and plasma chemical similarity in non-isothermal reactive plasmas

    International Nuclear Information System (INIS)

    Miethke, F.; Rutscher, A.; Wagner, H.E.

    2000-01-01

    With regard to the output of stable products the mode of operation of non-isothermal plasma chemical reactors shows physical and chemical well defined states, which represent limiting cases and may be interpreted as quasi-equilibrium states. The occurrence and the characteristics of these states, meanwhile more than once observed and described, are demonstrated by an instructive model reaction. Within the frame of the so-called Macroscopic Kinetics a central parameter is dominating the reactor operation. This result may be generalized and is linked up to the application of similarity principles for the reactor operation. After the general formulation of such principles, starting from the balance equations of particles and energy, a dimensionless similarity parameter is formulated, characterizing the composition of the effluent gas of the reactor. The applicability of this parameter is demonstrated by experimental examples. (Authors)

  9. Long-term degradation of chemical structures and mechanical properties in polyethylene induced by ion-beam irradiation

    International Nuclear Information System (INIS)

    Oka, T.; Hama, Y.

    2004-01-01

    The long-term degradation in polyethylene irradiated with ion beams was studied. We found the changes of the chemical structures and the mechanical properties with time storage. S-PE has a good resistance to ion-beam irradiation because the crystallinity and density were very low. (author)

  10. Double stratification effects in chemically reactive squeezed Sutterby fluid flow with thermal radiation and mixed convection

    Directory of Open Access Journals (Sweden)

    S. Ahmad

    2018-03-01

    Full Text Available A current analysis is carried out to study theoretically the mixed convection characteristics in squeezing flow of Sutterby fluid in squeezed channel. The constitutive equation of Sutterby model is utilized to characterize the rheology of squeezing phenomenon. Flow characteristics are explored with dual stratification. In flowing fluid which contains heat and mass transport, the first order chemical reaction and radiative heat flux affect the transport phenomenon. The systems of non-linear governing equations have been modulating which then solved by mean of convergent approach (Homotopy Analysis Method. The graphs are reported and illustrated for emerging parameters. Through graphical explanations, drag force, rate of heat and mass transport are conversed for different pertinent parameters. It is found that heat and mass transport rate decays with dominant double stratified parameters and chemical reaction parameter. The present two-dimensional examination is applicable in some of the engineering processes and industrial fluid mechanics. Keywords: Squeezing flow, Sutterby fluid model, Mixed convection, Double stratification, Thermal radiation, Chemical reaction

  11. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan

    2016-03-11

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  12. A Model to Couple Flow, Thermal and Reactive Chemical Transport, and Geo-mechanics in Variably Saturated Media

    Science.gov (United States)

    Yeh, G. T.; Tsai, C. H.

    2015-12-01

    This paper presents the development of a THMC (thermal-hydrology-mechanics-chemistry) process model in variably saturated media. The governing equations for variably saturated flow and reactive chemical transport are obtained based on the mass conservation principle of species transport supplemented with Darcy's law, constraint of species concentration, equation of states, and constitutive law of K-S-P (Conductivity-Degree of Saturation-Capillary Pressure). The thermal transport equation is obtained based on the conservation of energy. The geo-mechanic displacement is obtained based on the assumption of equilibrium. Conventionally, these equations have been implicitly coupled via the calculations of secondary variables based on primary variables. The mechanisms of coupling have not been obvious. In this paper, governing equations are explicitly coupled for all primary variables. The coupling is accomplished via the storage coefficients, transporting velocities, and conduction-dispersion-diffusion coefficient tensor; one set each for every primary variable. With this new system of equations, the coupling mechanisms become clear. Physical interpretations of every term in the coupled equations will be discussed. Examples will be employed to demonstrate the intuition and superiority of these explicit coupling approaches. Keywords: Variably Saturated Flow, Thermal Transport, Geo-mechanics, Reactive Transport.

  13. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Goncalves, Theo; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2016-01-01

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  14. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    Science.gov (United States)

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation.

  15. Multi-scale modelling of ions in solution: from atomistic descriptions to chemical engineering

    International Nuclear Information System (INIS)

    Molina, J.J.

    2011-01-01

    Ions in solution play a fundamental role in many physical, chemical, and biological processes. The PUREX process used in the nuclear industry to the treatment of spent nuclear fuels is considered as an example. For industrial applications these systems are usually described using simple analytical models which are fitted to reproduce the available experimental data. In this work, we propose a multi-scale coarse graining procedure to derive such models from atomistic descriptions. First, parameters for classical force-fields of ions in solution are extracted from ab-initio calculations. Effective (McMillan-Mayer) ion-ion potentials are then derived from radial distribution functions measured in classical molecular dynamics simulations, allowing us to define an implicit solvent model of electrolytes. Finally, perturbation calculations are performed to define the best possible representation for these systems, in terms of charged hard-sphere models. Our final model is analytical and contains no free 'fitting' parameters. It shows good agreement with the exact results obtained from Monte-Carlo simulations for the thermodynamic and structural properties. Development of a similar model for the electrolyte viscosity, from information derived from atomistic descriptions, is also introduced. (author)

  16. The ion dependent change in the mechanism of charge storage of chemically preintercalated bilayered vanadium oxide electrodes

    Science.gov (United States)

    Clites, Mallory; Pomerantseva, Ekaterina

    2017-08-01

    Chemical pre-intercalation is a soft chemistry synthesis approach that allows for the insertion of inorganic ions into the interlayer space of layered battery electrode materials prior to electrochemical cycling. Previously, we have demonstrated that chemical pre-intercalation of Na+ ions into the structure of bilayered vanadium oxide (δ-V2O5) results in record high initial capacities above 350 mAh g-1 in Na-ion cells. This performance is attributed to the expanded interlayer spacing and predefined diffusion pathways achieved by the insertion of charge-carrying ions. However, the effect of chemical pre-intercalation of δ-V2O5 has not been studied for other ion-based systems beyond sodium. In this work, we report the effect of the chemically preintercalated alkali ion size on the mechanism of charge storage of δ- MxV2O5 (M = Li, Na, K) in Li-ion, Na-ion, and K-ion batteries, respectively. The interlayer spacing of the δ-MxV2O5 varied depending on inserted ion, with 11.1 Å achieved for Li-preintercalated δ-V2O5, 11.4 Å for Na-preintercalated δ- V2O5, and 9.6 Å for K-preintercalated δ-V2O5. Electrochemical performance of each material has been studied in its respective ion-based system (δ-LixV2O5 in Li-ion cells, δ-NaxV2O5 in Na-ion cells, and δ-KxV2O5 in K-ion cells). All materials demonstrated high initial capacities above 200 mAh g-1. However, the mechanism of charge storage differed depending on the charge-carrying ion, with Li-ion cells demonstrating predominantly pseudocapacitive behavior and Naion and K-ion cells demonstrating a significant portion of capacity from diffusion-limited intercalation processes. In this study, the combination of increased ionic radii of the charge-carrying ions and decreased synthesized interlayer spacing of the bilayered vanadium oxide phase correlates to an increase in the portion of capacity attributed diffusion-limited charge-storage processes.

  17. Practical use of chemical probes for reactive oxygen species produced in biological systems by {gamma}-irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Min Hee; Moon, Yu Ran; Chung, Byung Yeoup; Kim, Jae-Sung [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Lee, Kang-Soo [Crop Production and Technology Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Cho, Jae-Young [Bio-environmental Science Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Kim, Jin-Hong [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)], E-mail: jhongkim@kaeri.re.kr

    2009-05-15

    Application of chemical probes, for detection of reactive oxygen species (ROS), was tested during {gamma}-irradiation. The ethanol/{alpha}-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) and 3,3'-diaminobenzidine (DAB) were structurally stable enough to detect {sup {center_dot}}OH and H{sub 2}O{sub 2}, increasingly generated by {gamma}-irradiation up to 1000 Gy. Interestingly, the production rate of H{sub 2}O{sub 2}, but not {sup {center_dot}}OH, during {gamma}-irradiation, was significantly different between in vitro systems of lettuce and spinach. These results suggest that 4-POBN and DAB could be utilized as a semi-quantitative probe to quantify {sup {center_dot}}OH and H{sub 2}O{sub 2}, produced by {gamma}-irradiation up to 1000 Gy.

  18. Chemical reactivity of self-organized alumina nanopores in aqueous medium

    International Nuclear Information System (INIS)

    Rocca, E.; Vantelon, D.; Gehin, A.; Augros, M.; Viola, A.

    2011-01-01

    This work is devoted to the characterization of the structure and chemistry of small self-organized nanopores of aluminum oxide in aqueous medium (diameter 4 /AlO 6 clusters is proposed to describe the amorphous oxide constituting the walls of the nanostructure. X-ray absorption near edge spectroscopy measurements, electrokinetic measurements and O 18 tracer experiments bring to light the structural changes and the specific diffusion mechanism in the nanometer network. Immersion in boiling water induces both the transformation of AlO 4 to AlO 6 clusters and the release of sulfate species by hydrolysis. Water molecules rapidly diffuse in the nanostructure, but ion diffusion is selective because of surface positive charges and overlap of the surface electric field in very small pores.

  19. Chemical environment of iron atoms in iron oxynitride films synthesized by reactive magnetron sputtering

    International Nuclear Information System (INIS)

    Grafoute, M.; Petitjean, C.; Rousselot, C.; Pierson, J.F.; Greneche, J.M.

    2007-01-01

    An iron oxynitride film was deposited on silicon and glass substrates by magnetron sputtering in an Ar-N 2 -O 2 reactive mixture. Rutherford back-scattering spectrometry was used to determine the film composition (Fe 1.06 O 0.35 N 0.65 ). X-ray diffraction revealed the formation of a face-centred cubic (fcc) structure with a lattice parameter close to that of γ'''-FeN. X-ray photoelectron spectroscopy showed the occurrence of Fe-N and Fe-O bonds in the film. The local environment of iron atoms studied by 57 Fe Moessbauer spectrometry at both 300 and 77 K gives clear evidence that the Fe 1.06 O 0.35 N 0.65 is not a mixture of iron oxide and iron nitride phases. Despite a small amount of an iron nitride phase, the main sample consists of an iron oxynitride phase with an NaCl-type structure where oxygen atoms partially substitute for nitrogen atoms, thus indicating the formation of a iron oxynitride with an fcc structure

  20. pH-Specific structural speciation of the ternary V(V)-peroxido-betaine system: a chemical reactivity-structure correlation.

    Science.gov (United States)

    Gabriel, C; Kioseoglou, E; Venetis, J; Psycharis, V; Raptopoulou, C P; Terzis, A; Voyiatzis, G; Bertmer, M; Mateescu, C; Salifoglou, A

    2012-06-04

    Vanadium involvement in cellular processes requires deep understanding of the nature and properties of its soluble and bioavailable forms arising in aqueous speciations of binary and ternary systems. In an effort to understand the ternary vanadium-H(2)O(2)-ligand interactions relevant to that metal ion's biological role, synthetic efforts were launched involving the physiological ligands betaine (Me(3)N(+)CH(2)CO(2)(-)) and H(2)O(2). In a pH-specific fashion, V(2)O(5), betaine, and H(2)O(2) reacted and afforded three new, unusual, and unique compounds, consistent with the molecular formulation K(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}]·H(2)O (1), (NH(4))(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}]·0.75H(2)O (2), and {Na(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}(2)]}(n)·4nH(2)O (3). All complexes 1-3 were characterized by elemental analysis; UV/visible, FT-IR, Raman, and NMR spectroscopy in solution and the solid state; cyclic voltammetry; TGA-DTG; and X-ray crystallography. The structures of 1 and 2 reveal the presence of unusual ternary dinuclear vanadium-tetraperoxido-betaine complexes containing [(V(V)═O)(O(2))(2)] units interacting through long V-O bonds. The two V(V) ions are bridged through the oxygen terminal of one of the peroxide groups bound to the vanadium centers. The betaine ligand binds only one of the two V(V) ions. In the case of the third complex 3, the two vanadium centers are not immediate neighbors, with Na(+) ions (a) acting as efficient oxygen anchors and through Na-O bonds holding the two vanadium ions in place and (b) providing for oxygen-containing ligand binding leading to a polymeric lattice. In 1 and 3, interesting 2D (honeycomb) and 1D (zigzag chains) topologies of potassium nine-coordinate polyhedra (1) and sodium octahedra (3), respectively, form. The collective physicochemical properties of the three ternary species 1-3 project the chemical role of the low molecular mass biosubstrate betaine in binding V

  1. chemical studies on the reactivity of some organic extractants for extraction and separation of certain elements from aqueous solutions

    International Nuclear Information System (INIS)

    Aly, M.M.I.

    2010-01-01

    Lanthanide elements such as lanthanum and neodymium are important elements in photo-electronic and metallurgical industries as well as in nuclear technology. The main constituents of the spent nuclear fuel are actinides like uranium, thorium and various fission products including lanthanides. The co-ordination compounds of the trivalent lanthanum and neodymium continues to be an active research area, which includes the specific spectroscopic and magnetic properties of rare earth ions and their applications as super molecular device, contrast-enhancing agents in magnetic resonance imaging, optical signal amplifiers and electroluminescent (EL) devices. Hence, the separation and purification of these elements is of great concern. Solvent extraction technique is employed to separate and purify rare earth elements in an industrial scale, but the separation of lanthanum and neodymium is a difficult task, as lanthanide ions exhibit similar chemical and physical properties. They have generally common and stable +3 oxidation state that requires synthesis of certain extractants which are able to extract them from different aqueous solutions. During the last twenty years, different publications have pointed out the remarkable properties of alkyl amide in the field of separation chemistry. These extractants are able to form stable co-ordination compounds with different metallic ions. In this concern, this thesis deals with the synthesis of different amide extractants namely N, N diethylacetoamide (DEAA), N, N Teteraphenyl malonamide (TPMA), N, N diphenylbenzamide (DPBA), N, N' diphenylacetoamide (DPAA), and N, N' Teteraethyl malonamide (TEMA), which were synthesized, characterized and compared with Aliquat-336 in kerosene for extraction and separation of La (III) and Nd (III). The effect of the different parameters affecting the extraction of these metals from aqueous nitric acid medium in the different systems has been studied in terms of shaking time, nitric acid, hydrogen

  2. 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.

  3. Tautomeric transformation of temozolomide, their proton affinities and chemical reactivities: A theoretical approach.

    Science.gov (United States)

    Sang-Aroon, Wichien; Ruangpornvisuti, Vithaya; Amornkitbamrung, Vittaya

    2016-05-01

    The gas-phase geometry optimizations of bare, mono- and dihydrated complexes of temozolomide isomers were carried out using density functional calculation at the M06-2X/6-31+G(d,p) level of the theory. The structures and protonation energies of protonated species of temozolomide are reported. Chemical indices of all isomers and protonated species are also reported. Energies, thermodynamic quantities, rate constants and equilibrium constants of tautomeric and rotameric transformations of all isomers I1↔TZM↔HIa↔HIb↔I2↔I3 in bare and hydrated systems were obtained. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Role of tip chemical reactivity on atom manipulation process in dynamic force microscopy

    Czech Academy of Sciences Publication Activity Database

    Sugimoto, Y.; Yurtsever, A.; Abe, M.; Morita, S.; Ondráček, Martin; Pou, P.; Perez, R.; Jelínek, Pavel

    2013-01-01

    Roč. 7, č. 8 (2013), s. 7370-7376 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GPP204/11/P578 Grant - others:GA AV ČR(CZ) M100101207 Institutional support: RVO:68378271 Keywords : noncontact atomic force microscopy * atomic manipulation * force spectroscopy * chemical interaction force * DFT simulations * nudged elastic band Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 12.033, year: 2013 http://pubs.acs.org/doi/abs/10.1021/nn403097p

  5. Molecular beam studies of hot atom chemical reactions: Reactive scattering of energetic deuterium atoms

    International Nuclear Information System (INIS)

    Continetti, R.E.; Balko, B.A.; Lee, Y.T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H 2 /minus/> DH + H and the substitution reaction D + C 2 H 2 /minus/> C 2 HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible. 18 refs., 9 figs

  6. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  7. Intra-/inter-laboratory validation study on reactive oxygen species assay for chemical photosafety evaluation using two different solar simulators.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Nakamura, Kazuichi; Ohno, Yasuo; Kojima, Hajime

    2014-06-01

    A previous multi-center validation study demonstrated high transferability and reliability of reactive oxygen species (ROS) assay for photosafety evaluation. The present validation study was undertaken to verify further the applicability of different solar simulators and assay performance. In 7 participating laboratories, 2 standards and 42 coded chemicals, including 23 phototoxins and 19 non-phototoxic drugs/chemicals, were assessed by the ROS assay using two different solar simulators (Atlas Suntest CPS series, 3 labs; and Seric SXL-2500V2, 4 labs). Irradiation conditions could be optimized using quinine and sulisobenzone as positive and negative standards to offer consistent assay outcomes. In both solar simulators, the intra- and inter-day precisions (coefficient of variation; CV) for quinine were found to be below 10%. The inter-laboratory CV for quinine averaged 15.4% (Atlas Suntest CPS) and 13.2% (Seric SXL-2500V2) for singlet oxygen and 17.0% (Atlas Suntest CPS) and 7.1% (Seric SXL-2500V2) for superoxide, suggesting high inter-laboratory reproducibility even though different solar simulators were employed for the ROS assay. In the ROS assay on 42 coded chemicals, some chemicals (ca. 19-29%) were unevaluable because of limited solubility and spectral interference. Although several false positives appeared with positive predictivity of ca. 76-92% (Atlas Suntest CPS) and ca. 75-84% (Seric SXL-2500V2), there were no false negative predictions in both solar simulators. A multi-center validation study on the ROS assay demonstrated satisfactory transferability, accuracy, precision, and predictivity, as well as the availability of other solar simulators. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Analytic description of the chemical erosion of graphite by hydrogen ions

    International Nuclear Information System (INIS)

    Roth, J.; Garcia-Rosales, C.

    1996-01-01

    One main concern about the use of graphite as a plasma facing material is the enhanced erosion, under hydrogen bombardment due to hydrocarbon formation. In view of the lifetime evaluation of plasma exposed carbon components and of impurity production in present and future machines such as ITER, an analytical expression for the erosion yield by chemical sputtering for the relevant energies, temperatures and incident fluxes is of special importance. An extrapolation to fluxes and energies relevant for high density divertor plasmas has not been possible up to now on the basis of semiempirical fits to laboratory data. Starting from a short review of the existing empirical formulas, recent detailed investigations of the atomistic processes for the thermally activated hydrocarbon emission are described, which enable the formulation of an improved analytical description including the ion flux as a parameter. The chemical erosion of graphite by hydrogen bombardment results from two processes: the thermally activated hydrocarbon emission, Y therm , and a surface process at low energies and low temperatures resulting from the kinetic ejection of surface hydrocarbon complexes from collisional energy transfer, Y surf . The new analytic description can be fitted well to the existing data for ion beam erosion, and extrapolation to divertor relevant fluxes is possible. At high ion fluxes the maximum of chemical erosion is shifted to higher temperatures, where annealing of damaged structures leads to a stronger reduction of Y therm than previously estimated. There are no data on a possible flux dependence of Y surf , leaving still some uncertainty in extrapolation. (author). 46 refs, 10 figs, 1 tab

  9. Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

    Science.gov (United States)

    Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

    2017-12-01

    Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

  10. MgB2 ultrathin films fabricated by hybrid physical chemical vapor deposition and ion milling

    Directory of Open Access Journals (Sweden)

    Narendra Acharya

    2016-08-01

    Full Text Available In this letter, we report on the structural and transport measurements of ultrathin MgB2 films grown by hybrid physical-chemical vapor deposition followed by low incident angle Ar ion milling. The ultrathin films as thin as 1.8 nm, or 6 unit cells, exhibit excellent superconducting properties such as high critical temperature (Tc and high critical current density (Jc. The results show the great potential of these ultrathin films for superconducting devices and present a possibility to explore superconductivity in MgB2 at the 2D limit.

  11. Chemical, spectroscopic, and ab initio modelling approach to interfacial reactivity applied to anion retention by siderite

    International Nuclear Information System (INIS)

    Badaut, V.

    2010-07-01

    Among the many radionuclides contained in high-level nuclear waste, 79 Se was identified as a potential threat to the safety of long term underground storage. However, siderite (FeCO 3 ) is known to form upon corrosion of the waste container, and the impact of this mineral on the fate of selenium was not accounted for. In this work, the interactions between selenium oxyanions - selenate and selenite - and siderite were investigated. To this end, both experimental characterizations (solution chemistry, X-ray Absorption Spectroscopy - XAS) and theoretical studies (ab initio modelling using Density Functional Theory - DFT ) were performed. Selenite and selenate (≤ 10 3 M) retention experiments by siderite suspensions (75 g/L ) at neutral pH in reducing glovebox (5 % H 2 ) showed that selenite is quantitatively immobilized by siderite after 48 h of reaction time, when selenate is only partly immobilized after 10 days. In the selenite case, XAS showed that immobilized selenium is initially present as Se(IV) probably sorbed on siderite surface. After 10 days of reaction, selenite ions are quantitatively reduced and form poorly crystalline elementary selenium. Selenite retention and reduction kinetics are therefore distinct. On the other hand, the fraction of immobilized selenate retained in the solid fraction does not appear to be significantly reduced over the probed timescale (10 days). For a better understanding of the reduction mechanism of selenite ions by siderite, the properties of bulk and perfect surfaces of siderite were modelled using DFT. We suggest that the properties of the valence electrons can be correctly described only if the symmetry of the fundamental state electronic density is lower than the experimental crystallographic symmetry. We then show that the retention of simple molecules as O 2 or H 2 O on siderite and magnesite (10 -14 ) perfect surfaces (perfect cleavage plane, whose surface energy is the lowest according to DFT) can be modelled with

  12. Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

    Science.gov (United States)

    Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

    2014-08-01

    It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

  13. Solvent extraction of some metal ions by dithiocarbamate types of chemically modified lipophilic chitosan

    International Nuclear Information System (INIS)

    Inoue, K.; Nakagawa, H.; Naganawa, H.; Tachimori, S.

    2001-01-01

    Chitosan is a basic polysaccharide containing primary amino groups with high reactivity. we prepared O,O'-decanoyl chitosan and dithiocarbamate O,O'-decanoyl chitosan; the former was soluble in chloroform and toluene, while latter was soluble not only these diluents but also in some aliphatic diluents such as hexane and kerosene which are employed in commercial scale solvent extraction. Solvent extraction by dithiocarbamate O,O'-decanoyl chitosan in kerosene was tested for some base metal ions from sulfuric acid solution. The sequence of selectivity for these metal ions was found to be as follows: Cu(II) >> Ni(II) > Cd(II) ∼ Fe(III) > Co(II) ∼ Zn(II). Copper(II) was quantitatively extracted at pH > 1 and quantitatively stripped with 2 M sulfuric acid solution. Solvent extraction of silver(I) and gold(III) from hydrochloric acid as well as lanthanides and americium(III) from nitrate solution were also tested. Americium was selectively extracted over trivalent lanthanides, suggesting a high possibility for the final treatment of high level radioactive wastes. (authors)

  14. Swift heavy ion induced modification in morphological and physico-chemical properties of tin oxide nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Jaiswal, Manoj Kumar [University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110 078 (India); Kanjilal, D. [Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110 067 (India); Kumar, Rajesh, E-mail: rajeshkumaripu@gmail.com [University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110 078 (India)

    2013-11-15

    Nanocomposite thin films of tin oxide (SnO{sub 2})/titanium oxide (TiO{sub 2}) were grown on silicon (1 0 0) substrates by electron beam evaporation deposition technique using sintered nanocomposite pellet of SnO{sub 2}/TiO{sub 2} in the percentage ratio of 95:5. Sintering of the nanocomposite pellet was done at 1300 °C for 24 h. The thicknesses of these films were measured to be 100 nm during deposition using piezo-sensor attached to the deposition chamber. TiO{sub 2} doped SnO{sub 2} nanocomposite films were irradiated by 100 MeV Au{sup 8+} ion beam at fluence range varying from 1 × 10{sup 11} ions/cm{sup 2} to 5 × 10{sup 13} ions/cm{sup 2} at Inter University Accelerator Center (IUAC), New Delhi, India. Chemical properties of pristine and ion irradiation modified thin films were characterized by Fourier Transform Infrared (FTIR) spectroscopy. FTIR peak at 610 cm{sup −1} confirms the presence of O–Sn–O bridge of tin (IV) oxide signifying the composite nature of pristine and irradiated thin films. Atomic Force Microscope (AFM) in tapping mode was used to study the surface morphology and grain growth due to swift heavy ion irradiation at different fluencies. Grain size calculations obtained from sectional analysis of AFM images were compared with results obtained from Glancing Angle X-ray Diffraction (GAXRD) measurements using Scherrer’s formulae. Phase transformation due to irradiation was observed from Glancing Angle X-ray Diffraction (GAXRD) results. The prominent 2θ peaks observed in GAXRD spectrum are at 30.67°, 32.08°, 43.91°, 44.91° and 52.35° in the irradiated films.

  15. Detection of Chemical/Biological Agents and Stimulants using Quadrupole Ion Trap Mass Spectrometry

    International Nuclear Information System (INIS)

    Harmon, S.H.; Hart, K.J.; Vass, A.A.; Wise, M.B.; Wolf, D.A.

    1999-01-01

    Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological agents is being developed for the U. S. Army under the Chemical and Biological Mass Spectrometer Block II program. The CBMS Block II is designed to optimize detection of both chemical and biological agents through the use of direct sampling inlets[I], a multi- ported sampling valve and a turbo- based vacuum system to support chemical ionization. Unit mass resolution using air as the buffer gas[2] has been obtained using this design. Software to control the instrument and to analyze the data generated from the instrument has also been newly developed. Detection of chemical agents can be accomplished. using the CBMS Block II design via one of two inlets - a l/ I 6'' stainless steel sample line -Chemical Warfare Air (CW Air) or a ground probe with enclosed capillary currently in use by the US Army - CW Ground. The Block II design is capable of both electron ionization and chemical ionization. Ethanol is being used as the Cl reagent based on a study indicating best performance for the Biological Warfare (BW) detection task (31). Data showing good signal to noise for 500 pg of methyl salicylate injected into the CW Air inlet, 50 ng of dimethylmethylphosphonate exposed to the CW Ground probe and 5 ng of methyl stearate analyzed using the pyrolyzer inlet were presented. Biological agents are sampled using a ''bio-concentrator'' unit that is designed to concentrate particles in the low micron range. Particles are collected in the bottom of a quartz pyrolyzer tube. An automated injector is being developed to deliver approximately 2 pL of a methylating reagent, tetramethylamonium- hydroxide to 'the collected particles. Pyrolysis occurs by rapid heating to ca. 55OOC. Biological agents are then characterized by their fatty acid methyl ester profiles and by other biomarkers. A library of ETOH- Cl/ pyrolysis MS data of microorganisms used for a recently published study[3] has been

  16. Chemical Mass Shifts in a Digital Linear Ion Trap as Analytical Identity of o-, m-, and p-Xylene.

    Science.gov (United States)

    Sun, Lulu; Xue, Bing; Huang, Zhengxu; Cheng, Ping; Ma, Li; Ding, Li; Zhou, Zhen

    2018-07-01

    Chemical mass shifts between isomeric ions of o-, m-, and p-xylene were measured using a digital linear ion trap, and the directions and values of the shifts were found to be correlated to the collision cross sections of the isomers. Both forward and reverse scans were used and the chemical shifts for each pair of isomers in scans of opposite directions were in opposite signs. Using different voltage settings (namely the voltage dividing ratio-VDR) of the ion trap allows adding high order field components in the quadrupole field and results in larger chemical mass shifts. The differential chemical mass shift which combined the shifts from forward and reverse scans doubled the amount of chemical shift, e.g., 0.077 Th between o- and p-xylene, enough for identification of the type of isomer without using an additional ion mobility spectrometer. The feature of equal and opposite chemical mass shifts also allowed to null out the chemical mass shift by calculating the mean m/z value between the two opposite scans and remove or reduce the mass error caused by chemical mass shift. Graphical Abstract ᅟ.

  17. Chemical Mass Shifts in a Digital Linear Ion Trap as Analytical Identity of o-, m-, and p-Xylene

    Science.gov (United States)

    Sun, Lulu; Xue, Bing; Huang, Zhengxu; Cheng, Ping; Ma, Li; Ding, Li; Zhou, Zhen

    2018-04-01

    Chemical mass shifts between isomeric ions of o-, m-, and p-xylene were measured using a digital linear ion trap, and the directions and values of the shifts were found to be correlated to the collision cross sections of the isomers. Both forward and reverse scans were used and the chemical shifts for each pair of isomers in scans of opposite directions were in opposite signs. Using different voltage settings (namely the voltage dividing ratio-VDR) of the ion trap allows adding high order field components in the quadrupole field and results in larger chemical mass shifts. The differential chemical mass shift which combined the shifts from forward and reverse scans doubled the amount of chemical shift, e.g., 0.077 Th between o- and p-xylene, enough for identification of the type of isomer without using an additional ion mobility spectrometer. The feature of equal and opposite chemical mass shifts also allowed to null out the chemical mass shift by calculating the mean m/z value between the two opposite scans and remove or reduce the mass error caused by chemical mass shift. [Figure not available: see fulltext.

  18. Coupling Chemical Kinetics and Flashes in Reactive, Thermal and Compositional Reservoir Simulation

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove

    2007-01-01

    of convergence and error test failures by more than 50% compared to direct integration without the new algorithm. To facilitate the algorithmic development we construct a virtual kinetic cell model. We use implicit one-step ESDIRK (Explicit Singly Diagonal Implicit Runge-Kutta) methods for integration...... of the kinetics. The kinetic cell model serves both as a tool for the development and testing of tailored solvers as well as a testbed for studying the interactions between chemical kinetics and phase behavior. A comparison between a Kvalue correlation based approach and a more rigorous equation of state based......Phase changes are known to cause convergence problems for integration of stiff kinetics in thermal and compositional reservoir simulations. We propose an algorithm for detection and location of phase changes based on discrete event system theory. The algorithm provides a robust way for handling...

  19. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies.

    Science.gov (United States)

    Schowalter, Steven J; Chen, Kuang; Rellergert, Wade G; Sullivan, Scott T; Hudson, Eric R

    2012-04-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates. © 2012 American Institute of Physics

  20. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies

    International Nuclear Information System (INIS)

    Schowalter, Steven J.; Chen Kuang; Rellergert, Wade G.; Sullivan, Scott T.; Hudson, Eric R.

    2012-01-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates.

  1. 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

  2. Purification process of natural graphite as anode for Li-ion batteries: chemical versus thermal

    Science.gov (United States)

    Zaghib, K.; Song, X.; Guerfi, A.; Rioux, R.; Kinoshita, K.

    The intercalation of Li ions in natural graphite that was purified by chemical and thermal processes was investigated. A new chemical process was developed that involved a mixed aqueous solution containing 30% H 2SO 4 and 30% NH xF y heated to 90 °C. The results of this process are compared to those obtained by heating the natural graphite from 1500 to 2400 °C in an inert environment (thermal process). The first-cycle coulombic efficiency of the purified natural graphite obtained by the chemical process is 91 and 84% after the thermal process at 2400 °C. Grinding the natural graphite before or after purification had no significant effect on electrochemical performance at low currents. However, grinding to a very small particle size before purification permitted optimization of the size distribution of the particles, which gives rise to a more homogenous electrode. The impurities in the graphite play a role as microabrasion agents during grinding which enhances its hardness and improves its mechanical properties. Grinding also modifies the particle morphology from a 2- to a 3-D structure (similar in shape to a potato). This potato-shaped natural graphite shows high reversible capacity at high current densities (about 90% at 1 C rate). Our analysis suggests that thermal processing is considerably more expensive than the chemical process to obtain purified natural graphite.

  3. Physico-chemical changes of the ground waters related to the 2011 El Hierro magmatic reactivation

    Science.gov (United States)

    Dionis, S.; Melián, G.; Padrón, E.; Padilla, G.; Nolasco, D.; Rodríguez, F.; Hernández, I.; Peraza, D.; Barrancos, J.; Hernández, P.; Calvo, D.; Pérez, N.

    2012-04-01

    The island of El Hierro (278 Km2), is the smallest, the southwesternmost and the youngest island (˜1.12 My) of the Canarian archipelago. The main geological characteristics of El Hierro consist on the presence of three convergent ridges of volcanic cones on a truncated trihedron shape and giant landslides between the three rift zones, being the most recent El Golfo on the northwest flank of the island. On July 2011 an anomalous seismic activity at Hierro Island started and suggested the initial stage of a volcanic unrest in the volcanic system. On October 10, after the occurrence of more than 10,000 earthquakes, a submarine eruption started. Evidences of this submarine volcanic eruption were visible on the sea surface to the south of La Restinga village, at the south of the island, in the form of large light-green coloured area, turbulent gas emission and the appearance of steamy volcanic fragments three days later. As part of its volcanic surveillance activities, the Instituto Volcanologico de Canarias (INVOLCAN) started a hydrogeochemical monitoring program on August 2011 in order to evaluate the temporal evolution of several physico-chemical parameters of the ground water system of El Hierro. Four observation sites were selected: three wells on the north of the island, where the seismic activity was located at the beginning of the volcano-seismic unrest (SIMO, FRON and PADO) and one horizontal well (gallery) in the south (TACO). Ground water sampling is being regularly collected, three times per week, at each observation site, and in-situ measurements of pH, conductivity and temperature measurements are performed. After 6 month of monitoring, no significant changes have been observed on pH and temperature measurements from all the observation sites. However, clear sharp decrease of conductivity was observed at SIMO on October 10 when the seismic tremor started. In addition, the strongest conductivity decrease pattern was observed later on at SIMO and PADO on

  4. 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

  5. Structural interpretation of chemically synthesized ZnO nanorod and its application in lithium ion battery

    International Nuclear Information System (INIS)

    Kundu, Samapti; Sain, Sumanta; Yoshio, Masaki; Kar, Tanusree; Gunawardhana, Nanda; Pradhan, Swapan Kumar

    2015-01-01

    Graphical abstract: - Highlights: • ZnO nanorods are synthesized at room temperature via a simple chemical route. • Growth direction of ZnO nanorods has been determined along 〈0 0 2〉. • ZnO nanorods constructed anode shows a high discharge capacity in first cycle. • It retains good reversible capacity compared to other ZnO morphologies. - Abstract: ZnO nanorods are synthesized at room temperature via a simple chemical route without using any template or capping agent and its importance is evaluated as a suitable candidate for anode material in lithium ion battery. Structural and microstructure characterizations of these nanorods are made by analyzing the X-ray diffraction data employing the Rietveld method of powder structure refinement. It reveals that the ZnO nanorods are grown up with a preferred orientation and elongated along 〈0 0 2〉. FESEM images reveal that these uniform cylindrical shaped nanorods are of different lengths and diameters. These synthesized ZnO nanorods are tested as an anode material for lithium ion batteries. The nano grain size of the ZnO rods results in less volume expansion and/or contraction during the alloying/de-alloying process and causes in good cyclability. In addition, synthesized ZnO nanorods deliver high charge/discharge capacities compared to other reported ZnO materials

  6. Structural interpretation of chemically synthesized ZnO nanorod and its application in lithium ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Kundu, Samapti; Sain, Sumanta [Materials Science Division, Department of Physics, The University of Burdwan, Golapbag, Burdwan 713104, West Bengal (India); Yoshio, Masaki [Advanced Research and Education Centre, Saga University, 1341 Yoga-machi, Saga 840-0047 (Japan); Kar, Tanusree [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India); Gunawardhana, Nanda, E-mail: nandagunawardhana@pdn.ac.lk [International Research Centre, Senate Building, University of Peradeniya, Peradeniya 20400 (Sri Lanka); Pradhan, Swapan Kumar, E-mail: skpradhan@phys.buruniv.ac.in [Materials Science Division, Department of Physics, The University of Burdwan, Golapbag, Burdwan 713104, West Bengal (India)

    2015-02-28

    Graphical abstract: - Highlights: • ZnO nanorods are synthesized at room temperature via a simple chemical route. • Growth direction of ZnO nanorods has been determined along 〈0 0 2〉. • ZnO nanorods constructed anode shows a high discharge capacity in first cycle. • It retains good reversible capacity compared to other ZnO morphologies. - Abstract: ZnO nanorods are synthesized at room temperature via a simple chemical route without using any template or capping agent and its importance is evaluated as a suitable candidate for anode material in lithium ion battery. Structural and microstructure characterizations of these nanorods are made by analyzing the X-ray diffraction data employing the Rietveld method of powder structure refinement. It reveals that the ZnO nanorods are grown up with a preferred orientation and elongated along 〈0 0 2〉. FESEM images reveal that these uniform cylindrical shaped nanorods are of different lengths and diameters. These synthesized ZnO nanorods are tested as an anode material for lithium ion batteries. The nano grain size of the ZnO rods results in less volume expansion and/or contraction during the alloying/de-alloying process and causes in good cyclability. In addition, synthesized ZnO nanorods deliver high charge/discharge capacities compared to other reported ZnO materials.

  7. Relationships between chemical compositions, microstructure, and corrosion properties in molybdenum ion implanted aluminum

    International Nuclear Information System (INIS)

    Kim, S.

    1986-01-01

    This thesis compares the corrosion properties of Al annealed after implantation with selected Mo concentrations to those of as-implanted Al with same Mo level and to pure Al. The principal results in this investigation are the improvement in the pitting corrosion resistance for Al implanted with Mo relative to pure Al in both the as-implanted and as-implanted-annealed state. The corrosion properties were related to the microstructures and chemical profiles in the surface-modified-regions. Potentiodynamic measurements indicate that stability of various species on the surface controls corrosion behavior in the Al-Mo system. Dual energy Mo implant procedure was used to produce a relatively thick ion implanted layer. The processing parameters were selected to produce specimen containing a continuous Al 12 Mo film with two different microstructures in the annealed material. The most improved pitting corrosion resistance was achieved in an as-implanted alloy which was implanted at 95 keV and then at 25 keV. This alloy was very resistant to pitting corrosion in a neutral aqueous solution containing 0.1 M chloride ion. Surface chemical analysis by Auger electron spectroscopy indicates that the role of Mo in inhibiting pitting corrosion is related to the formation of stable Mo oxide film

  8. 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.

  9. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim

    2013-10-01

    Rationale Polycyclic aromatic sulfur heterocycles (PASHs) are detrimental species for refining processes in petroleum industry. Current mass spectrometric Methods that determine their composition are often preceded by derivatization and dopant addition approaches. Different ionization Methods have different impact on the molecular assignment of complex PASHs. The analysis of such species under atmospheric pressure chemical ionization (APCI) is still considered limited due to uncontrolled ion generation with low- and high-mass PASHs. Methods The ionization behavior of a model mixture of five selected PASH standards was investigated using an APCI source with nitrogen as the reagent gas. A complex thiophenic fraction was separated from a vacuum gas oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same ionization pattern was observed for the real thiophenic sample. It was found that S1 class species were the major sulfur-containing species found in the VGO sample. These species indicated the presence of alkylated benzothiophenic (BT), dibenzothiophenic (DBT) and benzonaphthothiophenic (BNT) series that were detected by APCI-FTICR MS. CONCLUSIONS This study provides an established APCI-FTICR MS method for the analysis of complex PASHs. PASHs were detected without using any derivatization and without fragmentation. The method can be used for the analysis of S-containing crude oil samples. © 2013 John Wiley & Sons, Ltd.

  10. Chemical reactivity of precursor materials during synthesis of glasses used for conditioning high-level radioactive waste: Experiments and models

    International Nuclear Information System (INIS)

    Monteiro, A.

    2012-01-01

    The glass used to store high-level radioactive waste is produced by reaction of a solid waste residue and a glassy precursor (glass frit). The waste residue is first dried and calcined (to lose water and nitrogen respectively), then mixed with the glass frit to enable vitrification at high temperature. In order to obtain a good quality glass of constant composition upon cooling, the chemical reactions between the solid precursors must be complete while in the liquid state, to enable incorporation of the radioactive elements into the glassy matrix. The physical and chemical conditions during glass synthesis (e.g. temperature, relative proportions of frit and calcine, amount of radioactive charge) are typically empirically adjusted to obtain a satisfactory final product. The aim of this work is to provide new insights into the chemical and physical interactions that take place during vitrification and to provide data for a mathematical model that has been developed to simulate the chemical reactions. The consequences of the different chemical reactions that involve solid, liquid and gaseous phases are described (thermal effects, changes in crystal morphology and composition, variations in melt properties and structure). In a first series of experiments, a simplified analogue of the calcine (NaNO 3 -Al 2 O 3 ± MoO 3 /Nd 2 O 3 ) has been studied. In a second series of experiments, the simplified calcines have been reacted with a simplified glass frit (SiO 2 -Na 2 O-B 2 O 3 -Al 2 O 3 ) at high temperature. The results show that crystallization of the calcine may take place before interaction with the glass frit, but that the reactivity with the glass at high temperature is a function of the nature and stoichiometry of the crystalline phases which form at low temperature. The results also highlight how the mixing of the starting materials, the physical properties of the frit (viscosity, glass transition temperature) and the Na 2 O/Al 2 O 3 of the calcine but also its

  11. Chemical modifications of polymer films induced by high energy heavy ions

    International Nuclear Information System (INIS)

    Zhu Zhiyong; Sun Youmei; Liu Changlong; Liu Jie; Jin Yunfan

    2002-01-01

    Polymer films including polyethylene terephthalate (PET), polystyrene (PS) and polycarbonate (PC) were irradiated at room temperature with ions of 35 MeV/u 40 Ar, 25 MeV/u 84 Kr, 15.1 MeV/u 136 Xe and 11.4 MeV/u 238 U to fluences ranging from 9x10 9 to 5.5x10 12 ions/cm 2 . The radiation-induced chemical changes of the materials were investigated by Fourier-transform infrared (FTIR) and ultraviolet/visible spectroscopies. It is found that the absorbance in the ultraviolet and visible range induced by all irradiations follows a linear relationship with fluence. The radiation-induced absorbance normalized to one particle increases slowly with increasing of electronic energy loss below about 8 keV/nm followed by a sharp increase up to about 15 keV/nm above which saturation is reached. FTIR measurements reveal that the materials suffer serious degradation through bond breaking. The absorbance of the typical infrared bands decays exponentially with increase of ion fluence and the bond-disruption cross-section shows a sigmoid variation with electronic energy loss. In PET loss of crystallinity is attributed to the configuration transformation of the ethylene glycol residue from trans into the gauche. Alkyne end groups are induced in all the materials above certain electronic energy loss threshold, which is found to be about 0.8 keV/nm for PS and 0.4 keV/nm for PC. The production cross-section of alkyne end group increases with increasing of electronic energy loss and shows saturation at high electronic energy loss values. It is concluded that not only the physical processes but also the chemical processes of the energy deposition determine the modification of polymer

  12. Comparison of mass transfer coefficient approach and Nernst-Planck formulation in the reactive transport modeling of Co, Ni, and Ag removal by mixed-bed ion-exchange resins

    International Nuclear Information System (INIS)

    Bachet, Martin; Jauberty, Loic; De Windt, Laurent; Dieuleveult, Caroline de; Tevissen, Etienne

    2014-01-01

    Experiments performed under chemical and flow conditions representative of pressurized water reactors (PWR) primary fluid purification by ion exchange resins (Amberlite IRN9882) are modeled with the OPTIPUR code, considering 1D reactive transport in the mixed-bed column with convective/dispersive transport between beads and electro-diffusive transport within the boundary film around the beads. The effectiveness of the purification in these dilute conditions is highly related to film mass transfer restrictions, which are accounted for by adjustment of a common mass transfer coefficient (MTC) on the experimental initial leakage or modeling of species diffusion through the bead film by the Nernst-Planck equation. A detailed analysis of the modeling against experimental data shows that the Nernst-Planck approach with no adjustable parameters performs as well as, or better than, the MTC approach, particularly to simulate the chromatographic elution of silver by nickel and the subsequent enrichment of the solution in the former metal. (authors)

  13. 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.

  14. Synthesis, characterisation and chemical reactivity of some new binuclear dioxouranium(VI) complexes derived from organic diazo compounds (Preprint No. CT-33)

    International Nuclear Information System (INIS)

    Pujar, M.A.; Pirgonde, B.R.

    1988-02-01

    A new series of binuclear dioxouranium(VI) complexes of polydentatate diazo compounds have been synthesised and characterised adequately by analysis, physio-chemical techniques and reactivity of these complexes. The location of bonding site of ligands, stability of complexes and status of U-O bond and probable structures of these complexes have been discussed. (author). 10 refs

  15. Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

    Science.gov (United States)

    Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

  16. 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...

  17. A novel ion transport membrane reactor for fundamental investigations of oxygen permeation and oxy-combustion under reactive flow conditions

    KAUST Repository

    Kirchen, Patrick

    2013-01-01

    Ion transport membrane (ITM) reactors present an attractive technology for combined air separation and fuel conversion in applications such as syngas production, oxidative coupling or oxy-combustion, with the promise of lower capital and operating costs, as well higher product selectivities than traditional technologies. The oxygen permeation rate through a given ITM is defined by the membrane temperature and oxygen chemical potential difference across it. Both of these parameters can be strongly influenced by thermochemical reactions occurring in the vicinity of the membrane, though in the literature they are often characterized in terms of the well mixed product stream at the reactor exit. This work presents the development of a novel ITM reactor for the fundamental investigation of the coupling between fuel conversion and oxygen permeation under well defined fluid dynamic and thermodynamic conditions, including provisions for spatially resolved, in-situ investigations. A planar, finite gap stagnation flow reactor with optical and probe access to the reaction zone is used to facilitate in-situ measurements and cross-validation with detailed numerical simulations. Using this novel reactor, baseline measurements are presented to elucidate the impact of the sweep gas fuel (CH4) fraction on the oxygen permeation and fuel conversion. In addition, the difference between well-mixed gas compositions measured at the reactor outlet and those measured in the vicinity of the membrane surface are discussed, demonstrating the unique utility of the reactor. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

  18. The calculation of electron chemical potential and ion charge state and their influence on plasma conductivity in electrical explosion of metal wire

    International Nuclear Information System (INIS)

    Shi, Zongqian; Wang, Kun; Li, Yao; Shi, Yuanjie; Wu, Jian; Jia, Shenli

    2014-01-01

    The electron chemical potential and ion charge state (average ion charge and ion distribution) are important parameters in calculating plasma conductivity in electrical explosion of metal wire. In this paper, the calculating method of electron chemical potential and ion charge state is discussed at first. For the calculation of electron chemical potential, the ideal free electron gas model and Thomas-Fermi model are compared and analyzed in terms of the coupling constant of plasma. The Thomas-Fermi ionization model, which is used to calculate ion charge state, is compared with the method based on Saha equation. Furthermore, the influence of electron degenerated energy levels and ion excited states in Saha equation on the ion charge state is also analyzed. Then the influence of different calculating methods of electron chemical potential and ion charge state on plasma conductivity is discussed by applying them in the Lee-More conductivity model

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Chemical reactivities of the superconducting oxides, YBa2Cu3Oy and BiSrCaCu2Oy

    International Nuclear Information System (INIS)

    Toyama, Hisashi; Mizuno, Noritaka; Misono, Makoto

    1989-01-01

    The chemical reactivities of YBa 2 Cu 3 O y and BiSrCaCu 2 O y with various gases have been studied. It was found that large quantities of NO, CO, and NO 2 were rapidly absorbed (or intercalated) in the bulk of YBa 2 Cu 3 O y (T c : 90 K) at 573 K. The amount absorbed was in the order NO ∼ CO ∼ NO 2 > O 2 ∼ CO 2 > N 2 O ∼ 0. The amount for NO was more than two times the amount of YBa 2 Cu 3 O y in molar ratio and elongation by about 0.2 angstrom along c-axis was observed. NO absorbed was almost completely recovered as NO by the evacuation at 773 K. This absorption-desorption cycle proceeded reversively. The electronic resistivity at 573 K of YBa 2 Cu 3 O y increased upon the NO absorption and was restored by the evacuation at 773 K. CO was also absorbed rapidly accompanied by evolution of CO 2 . BiSrCaCu 2 O y did not absorb either NO or CO

  4. 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

  5. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O) n=1-5 clusters.

    Science.gov (United States)

    Linton, Kirsty A; Wright, Timothy G; Besley, Nicholas A

    2018-03-13

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + (H 2 O) n =1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO + (H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + (H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + (H 2 O) 5 [Formula: see text] H + (H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + (H 2 O) 5 Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + (H 2 O) 5 complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  6. Optical, structural, and chemical properties of CR-39 implanted with 5.2 MeV doubly charged carbon ions

    Science.gov (United States)

    Ali, Dilawar; Butt, M. Z.; Ishtiaq, Mohsin; Waqas Khaliq, M.; Bashir, Farooq

    2016-11-01

    Poly-allyl-diglycol-carbonate (CR-39) specimens were irradiated with 5.2 MeV doubly charged carbon ions using Pelletron accelerator. Ion dose was varied from 5 × 1013 to 5 × 1015 ions cm-2. Optical, structural, and chemical properties were investigated by UV-vis spectroscopy, x-ray diffractometer, and FTIR/Raman spectroscopy, respectively. It was found that optical absorption increases with increasing ion dose. Absorption edge shifts from UV region to visible region. The measured opacity values of pristine and ion implanted CR-39 range from 0.0519 to 4.7959 mm-1 following an exponential growth (9141%) with the increase in ion dose. The values of direct and indirect band gap energy decrease exponentially with an increase in ion dose by 59% and 71%, respectively. However, average refractive index in the visible region increases from 1.443 to 2.864 with an increase in ion dose, by 98%. A linear relation between band gap energy and crystallite size was observed. Both the number of carbon atoms in conjugation length and the number of carbon atoms per cluster increase linearly with the increase in ion dose. FTIR spectra showed that on C+2 ions irradiation, the intensity of all bands decreases gradually without appearance of any new band, indicating degradation of polymer after irradiation. Raman spectra revealed that the density of -CH2- group decreases on C+2 ions irradiation. However, the structure of CR-39 is completely destroyed on irradiation with ion dose 1 × 1015 and 5 × 1015 ions cm-2.

  7. An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules - application to a mixed reagent ion system for hydroperoxides and organic acids

    Science.gov (United States)

    Heikes, Brian G.; Treadaway, Victoria; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

    2018-04-01

    An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3-(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2-(H2O2) at m/z 66. O3 and NO give rise to species and cluster ions, CO3-(H2O) and NO3-(H2O), respectively, which interfere in the measurement of CH3OOH using O2-(CH3OOH) at m/z 80. The CO3-(H2O

  8. Extraction of metal ions using chemically modified silica gel: a PIXE analysis.

    Science.gov (United States)

    Jal, P K; Dutta, R K; Sudarshan, M; Saha, A; Bhattacharyya, S N; Chintalapudi, S N; K Mishra, B

    2001-08-30

    Organic ligand with carboxyhydrazide functional group was immobilised on the surface of silica gel and the metal binding capacity of the ligand-embedded silica was investigated. The functional group was covalently bonded to the silica matrix through a spacer of methylene groups by sequential reactions of silica gel with dibromobutane, malonic ester and hydrazine in different media. Surface area value of the modified silica was determined. The changes in surface area were correlated with the structural change of the silica surface due to chemical modifications. A mixture solution of metal ions [K(I),Cr(III),Co(II),Ni(II),Cu(II),Zn(II),Hg(II) and U(VI)] was treated with the ligand-embedded silica in 10(-3) M aqueous solution. The measurement of metal extraction capacity of the silica based ligand was done by multielemental analysis of the metal complexes thus formed by using Proton Induced X-ray Emission (PIXE) technique.

  9. Dielectric functions, chemical and atomic compositions of the near surface layers of implanted GaAs by In+ ions

    Science.gov (United States)

    Kulik, M.; Kołodyńska, D.; Bayramov, A.; Drozdziel, A.; Olejniczak, A.; Żuk, J.

    2018-06-01

    The surfaces of (100) GaAs were irradiated with In+ ions. The implanted samples were isobaric annealed at 800 °C and then of dielectric function, the surface atomic concentrations of atoms and also the chemical composition of the near surface layers in these implanted semiconductor samples were obtained. The following investigation methods were used: spectroscopic ellipsometry (SE), Rutherford backscattering spectrometry analyses (RBSA) and X-ray photoelectron spectroscopy (XPS) in the study of the above mentioned quantities, respectively. The change of the shape spectra of the dielectric functions at about 3.0 eV phonon energy, diffusion of In+ ions as well as chemical composition changes were observed after ion implantation and the thermal treatment. Due to displacement of Ga ions from GaAs by the In+ ions the new chemical compound InAs was formed. The relative amounts Ga2O3 and As2O3 ratio increase in the native oxide layers with the fluences increase after the thermal treatment of the samples. Additionally, it was noticed that the quantities of InO2 increase with the increasing values of the irradiated ions before thermal treatment.

  10. A new route to nanoscale tomographic chemical analysis: Focused ion beam-induced auger electron spectrosocpy

    Science.gov (United States)

    Parvaneh, Hamed

    This research project is aimed to study the application of ion-induced Auger electron spectroscopy (IAES) in combination with the characteristics of focused ion beam (FIB) microscopy for performing chemical spectroscopy and further evaluate its potential for 3-dimensional chemical tomography applications. The mechanism for generation of Auger electrons by bombarding ions is very different from its electron induced counterpart. In the conventional electron-induced Auger electron spectroscopy (EAES), an electron beam with energy typically in the range 1-10kV is used to excite inner-shell (core) electrons of the solid. An electron from a higher electron energy state then de-excites to fill the hole and the extra energy is then transferred to either another electron, i.e. the Auger electron, or generation of an X-ray (photon). In both cases the emitting particles have charac-teristic energies and could be used to identify the excited target atoms. In IAES, however, large excitation cross sections can occur by promotion of in-ner shell electrons through crossing of molecular orbitals. Originally such phenomenological excitation processes were first proposed [3] for bi-particle gas phase collision systems to explain the generation of inner shell vacancies in violent collisions. In addition to excitation of incident or target atoms, due to a much heavier mass of ions compared to electrons, there would also be a substantial momentum transfer from the incident to the target atoms. This may cause the excited target atom to recoil from the lattice site or alternatively sputter off the surface with the possibility of de-excitation while the atom is either in motion in the matrix or traveling in vacuum. As a result, one could expect differences between the spectra induced by incident electrons and ions and interpretation of the IAE spectra requires separate consideration of both excitation and decay processes. In the first stage of the project, a state-of-the-art mass

  11. Nuclear chemical method for preparation of free carbenium ions and radiochemical investigation of reactions of these particles

    International Nuclear Information System (INIS)

    Nefedov, V.D.; Sinotova, E.N.; Toropova, M.A.

    1980-01-01

    Tritium nuclear transformation (β-decay) in the composition of the molecules of hydrocarbons, appearance of primary molecular ions and formation of free carbenium ion are the main items of nuclear-chemical method of preparation of free carbenium ions. The method permits to prepare carbenium ions present in free state, i.e. without counterion and without solvate sheath of variou nitial localization of the charge. The rate of carbenium ion generation is strictly definite and does not depend upon outer conditions. The method suggested permits to prepare carbenium ions in all phases, study their reactions with individual substances in gaseous, liquid and solid states. The study of ion-molecular reactions is carried out using radiochemical method. The analysis of the products is made using the method of gaseous radiochromatography. Development of preparation techniques of carbenium ions and their analogues, study of the reactions of these particles with different classes of compounds, investigation of the effect of different factors upon procedure of ion-molecular reactions are the main directions of the investigations

  12. Ion Exchange Equilibrium and Kinetic Properties of Polyacrylate Films and Applications to Chemical Analysis and Environmental Decontamination

    Science.gov (United States)

    Tanner, Stephen P.

    1997-01-01

    One of the goals of the original proposal was to study how cross-linking affects the properties of an ion exchange material(IEM) developed at Lewis Research Center. However, prior to the start of this work, other workers at LERC investigated the effect of cross-linking on the properties of this material. Other than variation in the ion exchange capacity, the chemical characteristics were shown to be independent of the cross-linking agent, and the degree of cross-linking. New physical forms of the film were developed (film, supported film, various sizes of beads, and powder). All showed similar properties with respect to ion exchange equilibria but the kinetics of ion exchange depended on the surface area per unit mass; the powder form of the IEM exchanging much more rapidly than the other forms. The research performed under this grant was directed towards the application of the IEM to the analysis of metal ions at environmental concentrations.

  13. Dialkyldithiophosphoric acids - chemical properties and 5f and 4f elements ions extraction

    International Nuclear Information System (INIS)

    Pattee, D.

    1987-09-01

    This work is a contribution to the study of the properties of the dialkyldithiophosphoric acids and of the extraction of the 4f and 5f ions from weakly acidic nitrate and phosphate media. Following a complete bibliographic study, synthesis and purification of the di-2-ethylhexyl-dithiophosphoric acid (HDEHDTP) is studied. It is identified with chemical methods and spectroscopic methods (I.R., N.M.R., V.P.C.); its by products, the di-2-ethylhexyl (monothio) phosphoric acids (HDEHTP, HDEHP) are also identified and characterized. Stability against hydrolysis and radiolysis is determined. The extractive properties are studied for the 4f and 5f ions. The presence of a sulfur donor atom in HDEHDTP makes it inefficient for the extraction of trivalent lanthanides and actinides but brings out a certain selectivity for americium. For HDEHTP, the presence of an oxygen donor atom rubs out any selectivity and the extraction constants are greater. Selectivity of HDEHDTP is increased by TBP (tri-n-butylphosphate) in synergistic mixtures. The mechanism of extraction of hexavalent uranium from phosphoric medium is elucidated. A model is developed by NMR for the micellisation of the sodium salts of HDEHDTP, HDEHTP and HDEHP, and extrapolated it to the trivalent rare earth salts of the acids. The structures are verified by light scattering and low angle X-ray diffraction [fr

  14. Chemical Reactivity of Isoproturon, Diuron, Linuron, and Chlorotoluron Herbicides in Aqueous Phase: A Theoretical Quantum Study Employing Global and Local Reactivity Descriptors

    Directory of Open Access Journals (Sweden)

    Luis Humberto Mendoza-Huizar

    2015-01-01

    Full Text Available We have calculated global and local DFT reactivity descriptors for isoproturon, diuron, linuron, and chlorotoluron herbicides at the MP2/6-311++G(2d,2p level of theory. The results suggest that, in aqueous conditions, chlorotoluron, linuron, and diuron herbicides may be degraded by elimination of urea moiety through electrophilic attacks. On the other hand, electrophilic, nucleophilic, and free radical attacks on isoproturon may cause the elimination of isopropyl fragment.

  15. Global Structural Flexibility of Metalloproteins Regulates Reactivity of Transition Metal Ion in the Protein Core: An Experimental Study Using Thiol-subtilisin as a Model Protein.

    Science.gov (United States)

    Matsuo, Takashi; Kono, Takamasa; Shobu, Isamu; Ishida, Masaya; Gonda, Katsuya; Hirota, Shun

    2018-02-21

    The functions of metal-containing proteins (metalloproteins) are determined by the reactivities of transition metal ions at their active sites. Because protein macromolecular structures have several molecular degrees of freedom, global structural flexibility may also regulate the properties of metalloproteins. However, the influence of this factor has not been fully delineated in mechanistic studies of metalloproteins. Accordingly, we have investigated the relationship between global protein flexibility and the characteristics of a transition metal ion in the protein core using thiol-subtilisin (tSTL) with a Cys-coordinated Cu 2+ ion as a model system. Although tSTL has two Ca 2+ -binding sites, the Ca 2+ -binding status hardly affects its secondary structure. Nevertheless, guanidinium-induced denaturation and amide H/D exchange indicated the increase in the structural flexibility of tSTL by the removal of bound Ca 2+ ions. Electron paramagnetic resonance and absorption spectral changes have revealed that the protein flexibility determines the characteristics of a Cu 2+ ion in tSTL. Therefore, global protein flexibility should be recognized as an important factor that regulates the properties of metalloproteins. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Hydrogen determination in chemically delithiated lithium ion battery cathodes by prompt gamma activation analysis

    Science.gov (United States)

    Alvarez, Emilio, II

    2007-12-01

    Lithium ion batteries, due to their relatively high energy density, are now widely used as the power source for portable electronics. Commercial lithium ion cells currently employ layered LiCoO2 as a cathode but only 50% of its theoretical capacity can be utilized. The factors that cause the limitation are not fully established in the literature. With this perspective, prompt gamma-ray activation analysis (PGAA) has been employed to determine the hydrogen content in various oxide cathodes that have undergone chemical extraction of lithium (delithiation). The PGAA data is complemented by data obtained from atomic absorption spectroscopy (AAS), redox titration, thermogravimetric analysis (TGA), and mass spectroscopy to better understand the capacity limitations and failure mechanisms of lithium ion battery cathodes. As part of this work, the PGAA facility has been redesigned and reconstructed. The neutron and gamma-ray backgrounds have been reduced by more than an order of magnitude. Detection limits for elements have also been improved. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. The data indicates that while delithiated layered Li1- xCoO2, Li1-xNi 1/3Mn1/3Co1/3O2, and Li1- xNi0.5Mn0.5O2 take significant amounts of hydrogen into the lattice during deep extraction, orthorhombic Li 1-xMnO2, spinel Li1- xMn2O4, and olivine Li1- xFePO4 do not. Layered LiCoO2, LiNi 0.5Mn0.5O2, and LiNi1/3Mn1/3Co 1/3O2 have been further analyzed to assess their relative chemical instabilities while undergoing stepped chemical delithiation. Each system takes increasing amounts of protons at lower lithium contents. The differences are attributed to the relative chemical instabilities of the various cathodes

  17. Proton-sensing transistor systems for detecting ion leakage from plasma membranes under chemical stimuli.

    Science.gov (United States)

    Imaizumi, Yuki; Goda, Tatsuro; Schaffhauser, Daniel F; Okada, Jun-Ichi; Matsumoto, Akira; Miyahara, Yuji

    2017-03-01

    The membrane integrity of live cells is routinely evaluated for cytotoxicity induced by chemical or physical stimuli. Recent progress in bioengineering means that high-quality toxicity validation is required. Here, we report a pH-sensitive transistor system developed for the continuous monitoring of ion leakage from cell membranes upon challenge by toxic compounds. Temporal changes in pH were generated with high reproducibility via periodic flushing of HepG2 cells on a gate insulator of a proton-sensitive field-effect transistor with isotonic buffer solutions with/without NH 4 Cl. The pH transients at the point of NH 4 Cl addition/withdrawal originated from the free permeation of NH 3 across the semi-permeable plasma membranes, and the proton sponge effect produced by the ammonia equilibrium. Irreversible attenuation of the pH transient was observed when the cells were subjected to a membrane-toxic reagent. Experiments and simulations proved that the decrease in the pH transient was proportional to the area of the ion-permeable pores on the damaged plasma membranes. The pH signal was correlated with the degree of hemolysis produced by the model reagents. The pH assay was sensitive to the formation of molecularly sized pores that were otherwise not measurable via detection of the leakage of hemoglobin, because the hydrodynamic radius of hemoglobin was greater than 3.1nm in the hemolysis assay. The pH transient was not disturbed by inherent ion-transporter activity. The ISFET assay was applied to a wide variety of cell types. The system presented here is fast, sensitive, practical and scalable, and will be useful for validating cytotoxins and nanomaterials. The plasma membrane toxicity and hemolysis are widely and routinely evaluated in biomaterials science and biomedical engineering. Despite the recent development of a variety of methods/materials for efficient gene/drug delivery systems to the cytosol, the methodologies for safety validation remain unchanged in

  18. Zinc oxide nanostructures by chemical vapour deposition as anodes for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Laurenti, M., E-mail: marco.laurenti@iit.it [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Turin (Italy); Garino, N. [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Porro, S.; Fontana, M. [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Turin (Italy); Gerbaldi, C., E-mail: claudio.gerbaldi@polito.it [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Department of Applied Science and Technology – DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Turin (Italy)

    2015-08-15

    Highlights: • ZnO nanostructures are grown by simple chemical vapour deposition. • Polycrystalline nanostructured porous thin film is obtained. • Film exhibits stable specific capacity (∼400 mA h g{sup −1}) after prolonged cycling. • CVD-grown ZnO nanostructures show promising prospects as Li-ion battery anode. - Abstract: ZnO nanostructures are grown by a simple chemical vapour deposition method directly on a stainless steel disc current collector and successfully tested in lithium cells. The structural/morphological characterization points out the presence of well-defined polycrystalline nanostructures having different shapes and a preferential orientation along the c-axis direction. In addition, the high active surface of the ZnO nanostructures, which accounts for a large electrode/electrolyte contact area, and the complete wetting with the electrolyte solution are considered to be responsible for the good electrical transport properties and the adequate electrochemical behaviour, as confirmed by cyclic voltammetry and galvanostatic charge/discharge cycling. Indeed, despite no binder or conducting additives are used, when galvanostatically tested in lithium cells, after an initial decay, the ZnO nanostructures can provide a rather stable specific capacity approaching 70 μA h cm{sup −2} (i.e., around 400 mA h g{sup −1}) after prolonged cycling at 1 C, with very high Coulombic efficiency and an overall capacity retention exceeding 62%.

  19. Hybrid graphene oxide/DAB-Am-16 dendrimer: Preparation, characterization chemical reactivity and their electrocatalytic detection of L-Dopamine

    Science.gov (United States)

    Do Carmo, Devaney Ribeiro; Fernandes, Daniela Silvestrini

    2017-09-01

    Graphene oxide (GO) was chemically modified with a poly(propylene)imine Generation 3.0 dendrimer (DAB-Am-16). The characterization, structure and properties of hybrid graphene oxide/DAB-Am-16 dendrimer was studied by Raman spectroscopy, Fourier-Transforming Infrared Spectroscopy (FT-IR), X-Ray Photoelectron Spectroscopic (XPS), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis. After functionalized the hybrid material (GOD) can interact with copper and subsequently with hexacyanoferrate (III) ions (GODHCu). The GODHCu incorporated into a graphite paste electrode (20% w/w) was applied to an electrocatalytic detection of neurotransmitter L-dopamine using differential pulse voltammetry. The analytical curve showed a linear response in the concentration range from 1.0 × 10-7 to 1.0 × 10-5 mol L-1 with a corresponding equation Y(A) = 1.706 × 10-5 + 0.862 [L-dopamine] and a correlation coefficient r2 = 0.998. The detection limit was 6.36 × 10-7 mol L-1 with a relative standard deviation of ±4% (n = 3) and an amperometric sensitivity of 0.862 A/mol L-1.

  20. Deposition and characterization of zirconium nitride (ZrN) thin films by reactive magnetron sputtering with linear gas ion source and bias voltage

    Energy Technology Data Exchange (ETDEWEB)

    Kavitha, A.; Kannan, R. [Department of Physics, University College of Engineering, Anna University, Dindugal-624622 (India); Subramanian, N. Sankara [Department of Physics, Thiagarajar College of Engineering, Madurai -625015, Tamilnadu (India); Loganathan, S. [Ion Plating, Titan Industries Ltd., Hosur - 635126, Tamilnadu (India)

    2014-04-24

    Zirconium nitride thin films have been prepared on stainless steel substrate (304L grade) by reactive cylindrical magnetron sputtering method with Gas Ion Source (GIS) and bias voltage using optimized coating parameters. The structure and surface morphologies of the ZrN films were characterized using X-ray diffraction, atomic microscopy and scanning electron microscopy. The adhesion property of ZrN thin film has been increased due to the GIS. The coating exhibits better adhesion strength up to 10 N whereas the ZrN thin film with bias voltage exhibits adhesion up to 500 mN.

  1. Cross talk between increased intracellular zinc (Zn2+) and accumulation of reactive oxygen species in chemical ischemia.

    Science.gov (United States)

    Slepchenko, Kira G; Lu, Qiping; Li, Yang V

    2017-10-01

    Both zinc (Zn 2+ ) and reactive oxygen species (ROS) have been shown to accumulate during hypoxic-ischemic stress and play important roles in pathological processes. To understand the cross talk between the two of them, here we studied Zn 2+ and ROS accumulation by employing fluorescent probes in HeLa cells to further the understanding of the cause and effect relationship of these two important cellular signaling systems during chemical-ischemia, stimulated by oxygen and glucose deprivation (OGD). We observed two Zn 2+ rises that were divided into four phases in the course of 30 min of OGD. The first Zn 2+ rise was a transient, which was followed by a latent phase during which Zn 2+ levels recovered; however, levels remained above a basal level in most cells. The final phase was the second Zn 2+ rise, which reached a sustained plateau called Zn 2+ overload. Zn 2+ rises were not observed when Zn 2+ was removed by TPEN (a Zn 2+ chelator) or thapsigargin (depleting Zn 2+ from intracellular stores) treatment, indicating that Zn 2+ was from intracellular storage. Damaging mitochondria with FCCP significantly reduced the second Zn 2+ rise, indicating that the mitochondrial Zn 2+ accumulation contributes to Zn 2+ overload. We also detected two OGD-induced ROS rises. Two Zn 2+ rises preceded two ROS rises. Removal of Zn 2+ reduced or delayed OGD- and FCCP-induced ROS generation, indicating that Zn 2+ contributes to mitochondrial ROS generation. There was a Zn 2+ -induced increase in the functional component of NADPH oxidase, p47 phox , thus suggesting that NADPH oxidase may mediate Zn 2+ -induced ROS accumulation. We suggest a new mechanism of cross talk between Zn 2+ and mitochondrial ROS through positive feedback processes that eventually causes excessive free Zn 2+ and ROS accumulations during the course of ischemic stress. Copyright © 2017 the American Physiological Society.

  2. Physical and chemical changes induced by 70 MeV carbon ions in polyvinylidene difluoride (PVDF) polymer

    International Nuclear Information System (INIS)

    Virk, H.S.; Chandi, P.S.; Srivastava, A.K.

    2001-01-01

    Physical and chemical changes induced by 70 MeV carbon ions ( 12 C 5+ ) have been investigated in bulk polyvinylidene fluoride (PVDF) polymer. The induced changes have been studied with respect to their optical, chemical and structural response using UV-visible, FTIR and XRD techniques. The ion fluences ranging from 2.5x10 11 to 9x10 13 ions cm -2 have been used to study the irradiation effects. It has been observed that at the fluence of 9x10 13 ions cm -2 the PVDF sample became brittle and practically it was not possible to handle it for any further measurements. The recorded UV-visible spectra show that the optical absorption increases with increasing fluence, indicating maximum absorption at 200 nm. An interesting feature of UV-visible spectra is that dips change into peaks and vice versa with increase of fluence. In the FTIR spectra, development of new peaks at 1714 and 3692 cm -1 along with disappearance of peaks at 2363 and 3025 cm -1 and shifting of peak at 2984-2974 cm -1 have been observed due to high energy irradiation, indicating the chemical changes induced by 12 C 5+ . The diffraction pattern of PVDF indicates that this polymer is semi-crystalline in nature; a large decrease in the diffraction intensity indicates decrease in crystallinity. Increase in crystallite size has also been observed due to heavy ion irradiation

  3. Investigation of reactivity of inorganic free radicals relative to ferrocyanide- and octacyanomolybdate-ions in aqueous solutions by the method of pulse radiolysis

    International Nuclear Information System (INIS)

    Gogolev, A.V.; Fedoseev, A.M.; Makarov, I.F.; Pikaev, A.K.

    1989-01-01

    In aqueous solutions by the method of pulse radiolysis (dose per impulse-7.96-47.8 Gy, electron energy-5 MeV) the reactivity of Cl 2 - , Br 2 - , I 2 - , (SCN) 2 - , CO 3 - , SeO 3 - , SO 4 - radicals towards ferrocyanide ions and of Br 2 - , CO 3 - , SO 4 - radicals tawards octacyanomolybdate ions is studied. Linear dependence of rate constant logarithm of Cl 2 - , Br 2 - , I 2 - reactions with cyanide complexes on the difference of redox potentials of reacting particles ΔE 0 is obtained. Radicals containing oxygen react with cyanide complexes more rapidly than can be expected on the basis of ΔE 0 values. The effect of solution ionic strength, charge of reacting particles and radical nature on the reaction rate is discussed

  4. Optimization of time on CF{sub 4}/O{sub 2} etchant for inductive couple plasma reactive ion etching of TiO{sub 2} thin film

    Energy Technology Data Exchange (ETDEWEB)

    Adzhri, R., E-mail: adzhri@gmail.com; Fathil, M. F. M.; Ruslinda, A. R.; Gopinath, Subash C. B.; Voon, C. H.; Foo, K. L.; Nuzaihan, M. N. M.; Azman, A. H.; Zaki, M. [Institute of Nano Electronic Engineering (INEE), Universiti Malaysia Perlis (UniMAP), Perlis (Malaysia); Arshad, M. K. Md., E-mail: mohd.khairuddin@unimap.edu.my; Hashim, U.; Ayub, R. M. [Institute of Nano Electronic Engineering (INEE), Universiti Malaysia Perlis (UniMAP), Perlis (Malaysia); School of Microelectronic Engineering, Universiti Malaysia Perlis (UniMAP), Perlis (Malaysia)

    2016-07-06

    In this work, we investigate the optimum etching of titanium dioxide (TiO{sub 2}) using inductive couple plasma reactive ion etching (ICP-RIE) on our fabricated devices. By using a combination of CF{sub 4}/O{sub 2} gases as plasma etchant with ratio of 3:1, three samples of TiO{sub 2} thin film were etched with different time duration of 10 s, 15 s and 20 s. The ion bombardment of CF{sub 4} gases with plasma enhancement by O{sub 2} gas able to break the oxide bond of TiO{sub 2} and allow anisotropic etch profile with maximum etch rate of 18.6 nm/s. The sample was characterized by using optical profilometer to determine the depth of etched area and scanning electron microscopy (SEM) for etch profile characterization.

  5. Optimization of time on CF_4/O_2 etchant for inductive couple plasma reactive ion etching of TiO_2 thin film

    International Nuclear Information System (INIS)

    Adzhri, R.; Fathil, M. F. M.; Ruslinda, A. R.; Gopinath, Subash C. B.; Voon, C. H.; Foo, K. L.; Nuzaihan, M. N. M.; Azman, A. H.; Zaki, M.; Arshad, M. K. Md.; Hashim, U.; Ayub, R. M.

    2016-01-01

    In this work, we investigate the optimum etching of titanium dioxide (TiO_2) using inductive couple plasma reactive ion etching (ICP-RIE) on our fabricated devices. By using a combination of CF_4/O_2 gases as plasma etchant with ratio of 3:1, three samples of TiO_2 thin film were etched with different time duration of 10 s, 15 s and 20 s. The ion bombardment of CF_4 gases with plasma enhancement by O_2 gas able to break the oxide bond of TiO_2 and allow anisotropic etch profile with maximum etch rate of 18.6 nm/s. The sample was characterized by using optical profilometer to determine the depth of etched area and scanning electron microscopy (SEM) for etch profile characterization.

  6. 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.

  7. Regioisomers of octanoic acid-containing structured triacylglycerols analyzed by tandem mass spectrometry using ammonia negative ion chemical ionization

    DEFF Research Database (Denmark)

    Kurvinen, J.P.; Mu, Huiling; Kallio, H.

    2001-01-01

    Tandem mass spectrometry based on ammonia negative ion chemical ionization and sample introduction via direct exposure probe was applied to analysis of regioisomeric structures of octanoic acid containing structured triacylglycerols (TAG) of type MML, MLM, MLL, and LML (M, medium-chain fatty acid...

  8. Chemical sensors in natural water: peculiarities of behaviour of chalcogenide glass electrodes for determination of copper, lead and cadmium ions

    International Nuclear Information System (INIS)

    Seleznev, B.L.; Legin, A.V.; Vlasov, Yu.G.

    1996-01-01

    Specific features of chemical sensors (chalcogenide glass and crystal ion-selective electrodes) behaviour have been studied to determine copper (2), lead, cadmium and fluorine in the course of in situ measurements, including long-term uninterrupted testing, for solving the problem of inspection over natural water contamination. 16 refs., 3 figs., 2 tabs

  9. Chemical Properties of Dialkyl Halonium Ions (R2Hal+) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB11Hal11), Where Hal = F, Cl.

    Science.gov (United States)

    Stoyanov, Evgenii S

    2017-04-20

    Chloronium cations in their salts (C n H 2n+1 ) 2 Cl + {CHB 11 Cl 11 - }, with n = 1 to 3 and exceptionally stable carborane anions, are stable at ambient and elevated temperatures. The temperature at which they decompose to carbocations with HCl elimination (below 150 °C) decreases with the increasing n from 1 to 3 because of increasing ionicity of C-Cl bonds in the C-Cl + -C bridge. At room temperature, the salts of cations with n ≥ 4 [starting from t-Bu 2 Cl + or (cyclo-C 5 H 11 ) 2 Cl + ] are unstable and decompose. With decreasing chloronium ion stability, their ability to interact with chloroalkanes to form oligomeric cations increases. It was shown indirectly that unstable salt of fluoronium ions (CH 3 ) 2 F + (CHB 11 F 11 - ) must exist at low temperatures. The proposed (CH 3 ) 2 F + cation is much more reactive than the corresponding chloronium, showing at room temperature chemical properties expected of (CH 3 ) 2 Cl + at elevated temperatures.

  10. Study of chemically synthesized ZnO nano particles under a bio template using radioactive ion beam

    CERN Multimedia

    This is a project proposal to study nano sized semiconductor ZnO system, useful in biology and medicinal purposes, using radioactive ion beam from ISOLDE. Doping of the nano particles with Cu, Cd and Ga ions (in their variable valancy states) are expected to impart changes in the electrical structure and properties in the said system under study. The morphological changes, chemical environment, micro structure, electrical and optical properties of the nano size particles of ZnO system (developed under a bio template of folic acid) after the interaction with radioactive ion beam will be studied. The provision of perturbed angular correlation (PAC) study with respect to the changes in chemical environment, where ever possible will be attempted.

  11. Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

    Energy Technology Data Exchange (ETDEWEB)

    Aden, Bethany [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Kite, Camille M. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Hopkins, Benjamin W. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Zetterberg, Anna [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Lokitz, Bradley S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Ankner, John Francis [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Kilbey, S. Michael [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering

    2017-01-24

    Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on the size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.

  12. A novel ion transport membrane reactor for fundamental investigations of oxygen permeation and oxy-combustion under reactive flow conditions

    KAUST Repository

    Kirchen, Patrick; Apo, Daniel J.; Hunt, Anton; Ghoniem, Ahmed F.

    2013-01-01

    Ion transport membrane (ITM) reactors present an attractive technology for combined air separation and fuel conversion in applications such as syngas production, oxidative coupling or oxy-combustion, with the promise of lower capital and operating

  13. Chemical Interaction between U(VI) and Eu(III) ions on a Silica Surface

    International Nuclear Information System (INIS)

    Park, K. K.; Cha, W. S.; Cho, H. R.; Im, H. J.; Jung, E. C.

    2010-01-01

    Understanding the chemical behavior of actinide in groundwater flow is important for assessing the possibility of its migration with water flow in the radioactive waste disposal site. Precipitation/ dissolution in groundwater and adsorption/desorption onto a geological solid surface would determine its migration. The sorption in a geochemical system was expected to be a reaction on a naturally equilibrated surface. However, the construction of a waste disposal facility could disturb this equilibrium state, induce a new reaction environment and affect a nanoscopic surface reaction of actinide. Uranium is ubiquitous in the natural environment and a representative element in a nuclear fuel cycle and in a high level radioactive waste. In oxic environments, it is typically present as uranyl oxocation (UO 2 2+ ), which is easily adsorbed and thereby removed from a solution in the near neutral pH range. This adsorption would form a new surface condition to give an unexpected adsorption behavior for other actinide ions. Eu(III) frequently is used as a chemical analogue of Am(III) and Cm(III) in migration chemistry. The adsorption phenomena has been interpreted with the help of a SCM(surface complexation model). Some spectroscopic techniques such as EPR (Electron Paramagnetic Resonance), IR (InfraRed), EXAFS (Extended X-ray Absorption Fine Structure) and TRLFS (Time Resolved Laser Fluorescence Spectroscopy) have been used for the identification of a modeled adsorbing species. In the case of fluorescence elements, TRLFS has advantages over other techniques for its high sensitivity being proportional to laser source intensity and good selectivity depending on specific transition and lifetime. This technique can be applied to a species on a solid surface not absorbing light such as silica. U(VI) and Eu(III) have fluorescente properties reflecting their coordination structure. In this study, the interaction between U(VI) and Eu(III) on a silica surface was studied by a

  14. Anions Analysis in Ground and Tap Waters by Sequential Chemical and CO2-Suppressed Ion Chromatography

    Directory of Open Access Journals (Sweden)

    Glen Andrew D. De Vera

    2011-06-01

    Full Text Available An ion chromatographic method using conductivity detection with sequential chemical and CO2 suppression was optimized for the simultaneous determination of fluoride, chloride, bromide, nitrate,phosphate and sulfate in ground and tap water. The separation was done using an anion exchange column with an eluent of 3.2 mM Na2CO3 and 3.2 mM NaHCO3 mixture. The method was linear in the concentration range of 5 to 300 μg/L with correlation coefficients greater than 0.99 for the six inorganic anions. The method was also shown to be applicable in trace anions analysis as given by the low method detection limits (MDL. The MDL was 1μg/L for both fluoride and chloride. Bromide, nitrate, phosphate and sulfate had MDLs of 7 μg/L, 10 μg/L, 9 μg/L and 2 μg/L, respectively. Good precision was obtained as shown in the relative standard deviation of 0.1 to 12% for peak area and 0.1 to 0.3% for retention time. The sensitivity of the method improved with the addition of CO2 suppressor to chemical suppression as shown in the lower background conductivity and detection limits. The recoveries of the anions spiked in water at 300 μg/L level ranged from 100 to 104%. The method was demonstrated to be sensitive, accurate and precise for trace analysis of the six anions and was applied in the anions analysis in ground and tap waters in Malolos, Bulacan. The water samples were found to contain high concentrations of chloride of up to 476 mg/L followed by sulfate (38 mg/L, bromide (1 mg/L, phosphate (0.4 mg/L, fluoride (0.2 mg/L and nitrate (0.1 mg/L.

  15. Effect of oxygen gas and annealing treatment for magnetically enhanced reactive ion etched (Ba0.65,Sr0.35)TiO3 thin films

    International Nuclear Information System (INIS)

    Zhang Baishun; Quan Zuci; Zhang Tianjin; Guo Tao; Mo Shaobo

    2007-01-01

    Sol-gel-derived (Ba 0.65 ,Sr 0.35 )TiO 3 (BST) thin films were etched in CF 4 /Ar and CF 4 /Ar/O 2 plasmas using magnetically enhanced reactive ion etching technology. Experimental results show that adding appropriate O 2 to CF 4 /Ar can better the etching effects of BST films for the increase of etching rate and decrease of etched residues. The maximum etching rate is 8.47 nm/min when CF 4 /Ar/O 2 gas-mixing ratio is equal to 9/36/5. X-ray photoelectron spectroscopy (XPS) data confirm accumulation of reaction products on the etched surface due to low volatility of reaction products such as Ba and Sr fluorides, and these residues could be removed by annealing treatment. The exact peak positions and chemical shifts of the interested elements were deduced by fitting XPS narrow-scan spectra with symmetrical Gaussian-Lorentzian product function for Ba 3d, Sr 3d, and O 1s peaks, meanwhile asymmetrical Gaussian-Lorentzian sum function was used to fit Ti 2p doublet to adjust the multiple splitting and/or shake-up process of transition-metal Ti cations. Compared to the unetched counterparts, the etched Ba 3d 5/2 , Ba 3d 3/2 , Sr 3d 5/2 , Sr 3d 3/2 , Ti 2p 3/2 , Ti 2p 1/2 , and O 1s peaks shift towards higher binding energy regions by amounts of 1.31, 1.30, 0.60, 0.79, 0.09, 0.46, and 0.50 eV, respectively. While the etched Ti 2p 3/2 and Ti 2p 1/2 peaks have small chemical shifts for two reasons. One is that Ti fluoride (TiF z ) is mostly removed from the etched surface because of its higher volatility in the process of thermal desorption. The other is that there is a shift compensation between TiF z and the etched BST matrix in which Ti 4+ cations are partially reduced to form Ti x+ (0 0.65 ,Sr 0.35 )Ti 0.97 O 2.86 , (Ba 0.70 ,Sr 0.30 )Ti 0.24 O 1.39 , and (Ba 0.68 ,Sr 0.32 )Ti 0.95 O 2.74 , and then the average valence of Ti cations is estimated to be +3.84, +3.25, and +3.66 with respect to the electroneutrality principle, respectively. It is inferred that electrical

  16. Enhanced reactivation of UV-irradiated adenovirus 2 in HeLa cells treated with non-mutagenic chemical agents

    Energy Technology Data Exchange (ETDEWEB)

    Piperakis, S.M.; McLennan, A.G. (Liverpool Univ. (UK). Dept. of Biochemistry)

    1985-03-01

    Treatment of HeLa cells with ethanol and sodium arsenite, compounds which are known to elicit the heat-shock response, before infection with UV-irradiated adenovirus 2 has been found to result in the enhanced reactivation of the damaged virus in a manner similar to that obtained by pre-irradiation or heating of the cells. Enhanced reactivation may be the result of the inhibition of DNA synthesis caused by these agents since hydroxyurea also produced a significant enhancement.

  17. Chemical nature of implant-derived titanium(IV) ions in synovial fluid

    International Nuclear Information System (INIS)

    Silwood, Christopher J.L.; Grootveld, Martin

    2005-01-01

    Previous investigations have indicated a deleterious leakage of Ti(III) and/or Ti(IV) species from Ti-Al-V alloy joint prostheses into adjacent tissue, synovium or synovial fluid (SF) in vivo. In view of the importance of the particular chemical nature of such complexes in determining their biological activity, we have employed high field proton ( 1 H) NMR spectroscopy to 'speciate' Ti(IV) in inflammatory SF. Treatment of osteoarthritic SF samples with increasing concentrations of Ti(IV) (0.10-1.03 mM [TiO(C 2 O 4 ) 2 ] 2- ) gave rise to a specific broadening of the citrate proton resonances, indicating that this bioavailable oxygen-donor ligand plays an important role in complexing implant-derived Ti(IV). 1 H NMR analysis of Ti(IV)-loaded SF samples subsequently treated with a large excess of ascorbate (0.05 M) showed that this added Ti(IV) chelator was only poorly effective in removing this metal ion from Ti(IV)-citrate/Ti(IV)-oxycitrate complexes. The results obtained here provide evidence for complexation of the low-molecular-mass (non-protein-bound) fraction of implant-derived Ti(IV) by citrate in vivo

  18. Zinc Oxide-Based Self-Powered Potentiometric Chemical Sensors for Biomolecules and Metal Ions.

    Science.gov (United States)

    Israr-Qadir, Muhammad; Jamil-Rana, Sadaf; Nur, Omer; Willander, Magnus

    2017-07-19

    Advances in the miniaturization and portability of the chemical sensing devices have always been hindered by the external power supply problem, which has focused new interest in the fabrication of self-powered sensing devices for disease diagnosis and the monitoring of analytes. This review describes the fabrication of ZnO nanomaterial-based sensors synthesized on different conducting substrates for extracellular detection, and the use of a sharp borosilicate glass capillary (diameter, d = 700 nm) to grow ZnO nanostructures for intracellular detection purposes in individual human and frog cells. The electrocatalytic activity and fast electron transfer properties of the ZnO materials provide the necessary energy to operate as well as a quick sensing device output response, where the role of the nanomorphology utilized for the fabrication of the sensor is crucial for the production of the operational energy. Simplicity, design, cost, sensitivity, selectivity and a quick and stable response are the most important features of a reliable sensor for routine applications. The review details the extra- and intra-cellular applications of the biosensors for the detection and monitoring of different metallic ions present in biological matrices, along with the biomolecules glucose and cholesterol.

  19. Opto-chemical response of Makrofol-KG to swift heavy ion irradiation

    Indian Academy of Sciences (India)

    transform infrared spectroscopy; atomic force spectroscopy. PACS Nos ... [8–10], electron beam [11], neutrons [12] and heavy ions [13]. The present .... Makrofol detector with proton and Xe ions, respectively and reported that at higher doses.

  20. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim; Andersson, Jan T.; Mö ller, Isabelle; Amad, Maan H.; Witt, Matthí as; Sarathy, Mani

    2013-01-01

    oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same

  1. 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.

  2. 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.

  3. A model of chemical etching of olivine in the vicinity of the trajectory of a swift heavy ion

    Energy Technology Data Exchange (ETDEWEB)

    Gorbunov, S.A., E-mail: s.a.gorbunov@mail.ru [Lebedev Physical Institute of the Russian Academy of Sciences, Leninskij pr. 53, 119991 Moscow (Russian Federation); Rymzhanov, R.A. [Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna, Moscow Region (Russian Federation); Starkov, N.I. [Lebedev Physical Institute of the Russian Academy of Sciences, Leninskij pr. 53, 119991 Moscow (Russian Federation); Volkov, A.E. [Lebedev Physical Institute of the Russian Academy of Sciences, Leninskij pr. 53, 119991 Moscow (Russian Federation); Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna, Moscow Region (Russian Federation); National Research Centre ‘Kurchatov Institute’, Kurchatov Sq. 1, 123182 Moscow (Russian Federation); Malakhov, A.I. [Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna, Moscow Region (Russian Federation)

    2015-12-15

    Searching of superheavy elements, the charge spectra of heavy nuclei in Galactic Cosmic Rays was investigated within the OLYMPIA experiment using the database of etched ion tracks in meteorite olivine. Etching results in the formation of hollow syringe-like channels with diameters of 1–10 μm along the trajectories of these swift heavy ions (SHI). According to the activated complex theory, the local chemical activity is determined by an increase of the specific Gibbs energy of the lattice stimulated by structure transformations, long-range elastic fields, and interatomic bonds breaking generated in the vicinity of the ion trajectory. To determine the dependencies of the Gibbs free energy increase in SHI tracks in olivine on the mass, energy and charge of a projectile, we apply a multiscale model of excitation and relaxation of materials in the vicinity of the SHI trajectory (SHI tracks). Effect of spreading of fast electrons from the ion trajectory causing neutralization of metallic atoms resulting in an increase of the chemical activity of olivine at long distances from the ion trajectory (up to 5 μm) is estimated and discussed.

  4. Swelling behavior of ion exchange resins incorporated in tri-calcium silicate cement matrix: I. Chemical analysis

    International Nuclear Information System (INIS)

    Neji, M.; Bary, B.; Le Bescop, P.; Burlion, N.

    2015-01-01

    This paper presents the first part of a theoretical and experimental work aiming at modeling the chemo-mechanical behavior of composites made up of ion exchange resins (IER) solidified in a tri-calcium silicate cement paste (C_3S). Because of ion exchange processes, the volume change of the IER may cause internal pressures leading to the degradation of the material. In this study, a predictive modeling is developed for describing the chemical behavior of such material. It is based on thermodynamic equilibria to determine the evolution of the ion exchange processes, and the potential precipitation of portlandite in the composite. In parallel, a phenomenological study has been set up to understand chemical phenomena related to the swelling mechanisms. The model created has been finally implemented in a finite elements software; the simulation of a laboratory test has been performed and the results compared to experimental data. - Highlights: • Ion exchange theory to model the swelling behavior of Ion exchange resin. • Experimental phenomenon analysis about Chemo-mechanical interaction between IER and cement paste matrix. • Chemo-Transport modeling on a composite material made with IER embedded into cement paste matrix.

  5. Ab initio study of electron-ion structure factors in binary liquids with different types of chemical bonding

    International Nuclear Information System (INIS)

    Klevets, Ivan; Bryk, Taras

    2014-01-01

    Electron-ion structure factors, calculated in ab initio molecular dynamics simulations, are reported for several binary liquids with different kinds of chemical bonding: metallic liquid alloy Bi–Pb, molten salt RbF, and liquid water. We derive analytical expressions for the long-wavelength asymptotes of the partial electron-ion structure factors of binary systems and show that the analytical results are in good agreement with the ab initio simulation data. The long-wavelength behaviour of the total charge structure factors for the three binary liquids is discussed

  6. Chemical composition of sublates (difficultly soluble substances) which form on interaction of polyvalent metal ions with potassium alkylcarboxylate

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Skryleva, T.L.; Sazonova, V.F.

    1996-01-01

    The pH value is considered for its effect on chemical composition of sublates which form on interaction of fatty acid collectors (potassium alkylcarboxylate) with polyvalent ions of Ni, An, Cu and Be. It is shown that interaction of these ions with fatty acid collectors in weakly acid, neutral and weakly alkaline solutions is accompanied by formation of medium soaps. Acid soaps are formed in more acid solutions, while in more alkaline-basic soaps. Domains of stability for medium soaps of Ni, Zn, Cu and Be are determined. 17 refs.; 4 figs

  7. Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

    Science.gov (United States)

    Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

    2013-02-14

    Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

  8. Effect of silver ion-induced disorder on morphological, chemical and optical properties of poly (methyl methacrylate)

    Energy Technology Data Exchange (ETDEWEB)

    Arif, Shafaq, E-mail: sarif2005@gmail.com [Department of Physics, Lahore College for Women University, Lahore 54000 (Pakistan); Saleemi, Farhat [Department of Physics, Lahore College for Women University, Lahore 54000 (Pakistan); Rafique, M. Shahid [Department of Physics, University of Engineering & Technology, Lahore 54000 (Pakistan); Naab, Fabian; Toader, Ovidiu [Department of Nuclear Engineering and Radiological Sciences, Michigan Ion Beam Laboratory, University of Michigan, MI 48109-2104 (United States); Mahmood, Arshad; Aziz, Uzma [National Institute of Lasers & Optronics (NILOP), P.O. Nilore, Islamabad (Pakistan)

    2016-11-15

    Ion implantation is a versatile technique to tailor the surface properties of polymers in a controlled manner. In the present study, samples of poly (methyl methacrylate) (PMMA) have been implanted with 400 keV silver (Ag{sup +}) ion beam to various ion fluences ranging from 5 × 10{sup 13} to 5 × 10{sup 15} ions/cm{sup 2}. The effect of Ag{sup +} ion-induced disorder on morphological, chemical and optical properties of PMMA is analyzed using Atomic Force Microscope (AFM), Fourier transform infrared spectroscopy (FTIR) and ultraviolet–visible (UV–Vis) spectroscopy. Furthermore, the electrical conductivity of pristine and implanted PMMA is measured using four probe apparatus. The AFM images revealed the growth of nano-sized grainy structures and hillocks above the surface of implanted PMMA. The FTIR spectra confirmed the modifications in chemical structure of PMMA along with the formation of −C=C− carbon contents. The refractive index, extinction coefficient and photoconductivity of implanted PMMA have been found to increase as a function of ion fluence. Simultaneously, indirect optical band gap is reduced from 3.13 to 0.81 eV at a relatively high fluence (5 × 10{sup 15} ions/cm{sup 2}). A linear correlation has been established between the band gap and Urbach energies. Moreover, the electrical conductivity of Ag{sup +} implanted PMMA has increased from 2.14 × 10{sup −10} (pristine) to 9.6 × 10{sup −6} S/cm.

  9. Physico-chemical modification of polyethersulphone induced by high energy proton, C+ and Ne6+ ions

    International Nuclear Information System (INIS)

    Vinodh Kumar, S.; Biswavarathi, V.; Jal, P.; Dey, K.; Krishna, J.B.M.; Saha, A.

    2004-01-01

    Polyehersulphone (PES) was irradiated with 4 MeV proton, 3.6 MeV C + and 145 MeV Ne 6+ ions at different ion fluences. The ion induced spectral changes were analyzed by UV-visible and fluorescence spectroscopy. The increase in optical absorption, which shifts gradually from near UV to the visible region with increase in fluence for the three different types of bombarding ions was observed. A significant loss in fluorescence intensity with increase in fluence for three different ions was observed. (author)

  10. Methods and apparatus for cleaning objects in a chamber of an optical instrument by generating reactive ions using photon radiation

    Science.gov (United States)

    Klebanoff, Leonard E.; Delgado, Gildardo R.; Hollenshead, Jeromy T.; Umstadter, Karl R.; Starodub, Elena; Zhuang, Guorong V.

    2015-10-13

    An optical instrument, including a chamber, an object exposed to an interior of the chamber, a source of low-pressure gas, the gas comprising at least one of low-pressure molecular hydrogen gas, low-pressure molecular oxygen and a low-pressure noble gas, the source of low pressure gas being fluidly coupled to the chamber, a low voltage source electrically coupled between the object and a remaining portion of the instrument that is exposed to the interior of the chamber so as to maintain the object at a low voltage relative to the remaining portion, and an EUV/VUV light source adapted to direct EUV/VUV light through the low pressure gas in the chamber onto the object. In such a system, when the EUV/VUV light source is activated ions of the low-pressure gas are formed and directed to the object. The ions may be ions of Hydrogen, Oxygen or a noble gas.

  11. Microwave-assisted reactive sintering and lithium ion conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

    Science.gov (United States)

    Hallopeau, Leopold; Bregiroux, Damien; Rousse, Gwenaëlle; Portehault, David; Stevens, Philippe; Toussaint, Gwenaëlle; Laberty-Robert, Christel

    2018-02-01

    Li1.3Al0.3Ti1.7(PO4)3 (LATP) materials are made of a three-dimensional framework of TiO6 octahedra and PO4 tetrahedra, which provides several positions for Li+ ions. The resulting high ionic conductivity is promising to yield electrolytes for all-solid-state Li-ion batteries. In order to elaborate dense ceramics, conventional sintering methods often use high temperature (≥1000 °C) with long dwelling times (several hours) to achieve high relative density (∼90%). In this work, an innovative synthesis and processing approach is proposed. A fast and easy processing technique called microwave-assisted reactive sintering is used to both synthesize and sinter LATP ceramics with suitable properties in one single step. Pure and crystalline LATP ceramics can be achieved in only 10 min at 890 °C starting from amorphous, compacted LATP's precursors powders. Despite a relative density of 88%, the ionic conductivity measured at ambient temperature (3.15 × 10-4 S cm-1) is among the best reported so far. The study of the activation energy for Li+ conduction confirms the high quality of the ceramic (purity and crystallinity) achieved by using this new approach, thus emphasizing its interest for making ion-conducting ceramics in a simple and fast way.

  12. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene.

    Science.gov (United States)

    Irving, Roy M; Pinkerton, Marie E; Elfarra, Adnan A

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague-Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S(2)-S(3) segments) while DCVCS primarily affected the outer cortical proximal tubules (S(1)-S(2) segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37°C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

    Science.gov (United States)

    Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

    2018-03-01

    Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

  14. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene

    International Nuclear Information System (INIS)

    Irving, Roy M.; Pinkerton, Marie E.; Elfarra, Adnan A.

    2013-01-01

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S 2 –S 3 segments) while DCVCS primarily affected the outer cortical proximal tubules (S 1 –S 2 segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity

  15. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene

    Energy Technology Data Exchange (ETDEWEB)

    Irving, Roy M. [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Pinkerton, Marie E. [Department of Pathobiological Sciences, University of Wisconsin-Madison, Madison, WI 53706 (United States); Elfarra, Adnan A., E-mail: elfarra@svm.vetmed.wisc.edu [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Department of Comparative Biosciences, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S{sub 2}–S{sub 3} segments) while DCVCS primarily affected the outer cortical proximal tubules (S{sub 1}–S{sub 2} segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity.

  16. 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.

  17. Sub-micrometer-scale patterning on Zr-based metallic glass using focused ion beam irradiation and chemical etching

    Energy Technology Data Exchange (ETDEWEB)

    Kawasegi, Noritaka [Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Morita, Noboru [Graduate School of Science and Engineering for Research, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Yamada, Shigeru [Graduate School of Science and Engineering for Research, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Takano, Noboru [Graduate School of Science and Engineering for Research, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Oyama, Tatsuo [Department of Mechanical and Intellectual Systems Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Ashida, Kiwamu [Advanced Manufacturing Research Institute, National Institute of Advanced Industrial Science and Technology, 1-2-1 Namiki, Tsukuba, Ibaraki 305-8564 (Japan); Momota, Sadao [Department of Intelligent Mechanical Systems Engineering, Kochi University of Technology, 185 Tosayamada, Kochi 782-8502 (Japan); Taniguchi, Jun [Department of Applied Electronics, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510 (Japan); Miyamoto, Iwao [Department of Applied Electronics, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510 (Japan); Ofune, Hitoshi [YKK Corporation, 200 Yoshida, Kurobe, Toyama 938-8601 (Japan)

    2007-09-19

    This report describes a method of sub-micrometer-scale rapid patterning on a Zr-based metallic glass surface using a combination of focused ion beam irradiation and wet chemical etching. We found that a Zr-based metallic glass surface irradiated with Ga{sup +} ions could be selectively etched; a concave structure with a width and depth of several tens to hundreds of nanometers rapidly formed in the irradiated area. Moreover, we determined that the etching was enhanced by the presence of Ga{sup +} ions rather than a change in the crystal structure, and the structure could be fabricated while the substrate remained amorphous. The shape of the structure was principally a function of the dose and the etch time.

  18. Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon [Chungnam National Univ., Daejeon (Korea, Republic of); Cho, Soo Gyeong; Goh, Eun Mee [Agency for Defense Development, Daejeon (Korea, Republic of); Lee, Sungman; Koh, Sungsuk [Sensor Tech Inc., Seoul (Korea, Republic of)

    2013-12-15

    Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H]{sup -} for TNT and DNT or [M]{sup ·-}. for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO]{sup -}. These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available.

  19. Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

    International Nuclear Information System (INIS)

    Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sungsuk

    2013-01-01

    Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H] - for TNT and DNT or [M] ·- . for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO] - . These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available

  20. Optimization of LiCoO2 powder extraction process from cathodes of lithium-ion batteries by chemical dissolution

    OpenAIRE

    Lucas Evangelista Sita; Stephany Pires da Silva; Paulo Rogério Catarini da Silva; Alexandre Urbano; Jair Scarminio

    2015-01-01

    A chemical process has been applied to extract LiCoO2 powder from cathodes of spent lithium-ion batteries by dissolution of the binder that agglutinate the powder particle each other as well to the Al collector surface. As solvents dimethylformamide (DMF) and N-methyilpirrolidone (NMP) were employed and the variables, cathode area, solution temperature, ultrasound bath power and solution stirring were chosen to optimize the extraction process. NMP solutions presented best results for powder e...

  1. In-medium Modifications of Hadron Masses and Chemical Freeze-out in Ultra-relativistic Heavy-ion Collisions

    International Nuclear Information System (INIS)

    Florkowski, W.; Broniowski, W.

    1999-10-01

    We confront the hypothesis of chemical freeze-out in ultra-relativistic heavy-ion collisions with the hypothesis of large modifications of hadron masses in nuclear medium. We find that the thermal-model predictions for the ratios of particle multiplicities are sensitive to the values of in-medium hadronic masses. In particular, the π + /p ratio decreases by 35% when the masses of all hadrons (except for pseudo-Goldstone bosons) are scaled down by 30%. (author)

  2. Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air.

    Science.gov (United States)

    Urabe, Tatsuya; Takahashi, Kazuya; Kitagawa, Michiko; Sato, Takafumi; Kondo, Tomohide; Enomoto, Shuichi; Kidera, Masanori; Seto, Yasuo

    2014-01-01

    A portable mass spectrometer with an electron cyclotron resonance ion source (miniECRIS-MS) was developed. It was used for in situ monitoring of trace amounts of chemical warfare agents (CWAs) in atmospheric air. Instrumental construction and parameters were optimized to realize a fast response, high sensitivity, and a small body size. Three types of CWAs, i.e., phosgene, mustard gas, and hydrogen cyanide were examined to check if the mass spectrometer was able to detect characteristic elements and atomic groups. From the results, it was found that CWAs were effectively ionized in the miniECRIS-MS, and their specific signals could be discerned over the background signals of air. In phosgene, the signals of the 35Cl+ and 37Cl+ ions were clearly observed with high dose-response relationships in the parts-per-billion level, which could lead to the quantitative on-site analysis of CWAs. A parts-per-million level of mustard gas, which was far lower than its lethal dosage (LCt50), was successfully detected with a high signal-stability of the plasma ion source. It was also found that the chemical forms of CWAs ionized in the plasma, i.e., monoatomic ions, fragment ions, and molecular ions, could be detected, thereby enabling the effective identification of the target CWAs. Despite the disadvantages associated with miniaturization, the overall performance (sensitivity and response time) of the miniECRIS-MS in detecting CWAs exceeded those of sector-type ECRIS-MS, showing its potential for on-site detection in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Induction of molecular endpoints by reactive oxygen species in human lung cells predicted by physical chemical properties of engineered nanoparticles

    Science.gov (United States)

    A series of six titanium dioxide and two cerium oxide engineered nanomaterials were assessed for their ability to induce cytotoxicity, reactive oxygen species (ROS), and various types of DNA and protein damage in human respiratory BEAS-2B cells exposed in vitro for 72 hours at se...

  4. Detection of methamphetamine in the presence of nicotine using in situ chemical derivatization and ion mobility spectrometry.

    Science.gov (United States)

    Ochoa, Mariela L; Harrington, Peter B

    2004-02-15

    The detection of methamphetamine in the presence of nicotine has been successfully accomplished using in situ chemical derivatization with propyl chloroformate as the derivatization reagent and ion mobility spectrometry (IMS). The rapid detection of methamphetamine is important for forensic scientists in order to establish a chain of evidence and link criminals to the crime scene. Nicotine is pervasive in clandestine drug laboratories from cigarette smoke residue. It has been demonstrated that nicotine obscures the methamphetamine peaks in ion mobility spectrometers due to their similar charge affinities and ion mobilities, which makes their detection a challenging task. As a consequence, false positive or negative responses may arise. In situ chemical derivatization poses as a sensitive, accurate, and reproducible alternative to remove the nicotine background when detecting nanogram amounts of methamphetamine. The derivatization agent was coated onto the sample disk, and the derivatization product corresponding to propyl methamphetamine carbamate was detected. In the present study, in situ chemical derivatization was demonstrated to be a feasible method to detect methamphetamine hydrochloride as the carbamate derivative, which was baseline-resolved from the nicotine peak. Alternating least squares (ALS) was used to model the datasets. A mixture containing both compounds revealed reduced mobilities of 1.61 cm(2)/V.s and 1.54 cm(2)/V.s for methamphetamine and nicotine, respectively. The reduced mobility of propyl methamphetamine carbamate was found at 1.35 cm(2)/V.s.

  5. 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

  6. 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

  7. 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

  8. Deep Reactive Ion Etching (DRIE) of High Aspect Ratio SiC Microstructures using a Time-Multiplexed Etch-Passivate Process

    Science.gov (United States)

    Evans, Laura J.; Beheim, Glenn M.

    2006-01-01

    High aspect ratio silicon carbide (SiC) microstructures are needed for microengines and other harsh environment micro-electro-mechanical systems (MEMS). Previously, deep reactive ion etching (DRIE) of low aspect ratio (AR less than or = 1) deep (greater than 100 micron) trenches in SiC has been reported. However, existing DRIE processes for SiC are not well-suited for definition of high aspect ratio features because such simple etch-only processes provide insufficient control over sidewall roughness and slope. Therefore, we have investigated the use of a time-multiplexed etch-passivate (TMEP) process, which alternates etching with polymer passivation of the etch sidewalls. An optimized TMEP process was used to etch high aspect ratio (AR greater than 5) deep (less than 100 micron) trenches in 6H-SiC. Power MEMS structures (micro turbine blades) in 6H-SiC were also fabricated.

  9. Study of a new hybrid process combining slurry infiltration and Reactive Chemical Vapour Infiltration for the realisation of Ceramic Matrix Composites

    International Nuclear Information System (INIS)

    Ledain, Olivier

    2014-01-01

    Ceramic matrix composites were originally developed for aerospace,military aeronautics or energy applications thanks to their good properties at high temperature. They are generally made by Chemical Vapor Infiltration (CVI). A new short hybrid process combining fiber preform slurry impregnation of ceramic powders with an innovative Reactive CVI (RCVI) route is proposed to reduce the production time. This route is based on the combination of Reactive Chemical Vapour Deposition (RCVD), which is often used to deposit coatings on fibres, with the Chemical Vapor Infiltration (CVI).In RCVD, the absence of one element of the deposited carbide in the initial gas phase involves the consumption/conversion of the solid substrate. In this work, the RCVD growth and the associated consumption were studied with different parameters in the Ti-H-Cl-C chemical system. The study has been completed with the chemical products analysis, combining XRD, XPS and FTIR. Then, the partial conversion of sub-micrometer carbon powders into titanium carbide and the consolidation of green bodies by RCVI from H 2 /TiCl 4 gaseous infiltration were studied. The residual porosity and the final TiC content were measured in the bulk of the infiltrated powders by image analysis from scanning electron microscopy. Depending on temperature, few hundred micrometers-depth infiltrations are obtained.Finally, the results have been transposed to the RCVI into CMC-type pre-forms. Despite a minimal TiC content of 25% in the overall preform, the results shown a bad homogeneity of the infiltration and a poor cohesion of fibres with RCVI consolidated powder of their environment. (author) [fr

  10. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    Science.gov (United States)

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  11. Study by γ radiolysis and pulsed radiolysis of the reactivity of the superoxide ion in the oxyhemoglobin-methemoglobin system

    International Nuclear Information System (INIS)

    Haristoy, Didier.

    1976-01-01

    γ radiolysis of aqueous solutions of methemoglobin (MetHb) in the presence of formate ions, shows that only 25% of the total protein is reduced in oxyhemoglobin (HbO 2 ) by superoxide ions O 2 - according to the reaction MetHb+O 2 - →HbO 2 . The result can be attributed neither to the reactions of O 2 - with HbO 2 , nor the oxidation of HbO 2 by H 2 O 2 produced in the radiolysis of water and by dismutation of O 2 - . Pulse radiolysis studies of this reaction strongly suggest the formation of a transient complex 'MetHbO 2 - ' during the reaction. In addition to the well known self-oxidation of HbO 2 , these results show the existence of an equilibrium between HbO 2 and MetHb+O 2 - . Such an equilibrium could give rise, 'in vivo' to a nearly steady concentration of superoxide ions which could initiate a reaction favoring oxidation by oxygen [fr

  12. A Novel Ion Exchange System to Purify Mixed ISS Waste Water Brines for Chemical Production and Enhanced Water Recovery

    Science.gov (United States)

    Lunn, Griffin; Spencer, LaShelle; Ruby, Anna-Maria; McCaskill, Andrew

    2014-01-01

    Current International Space Station water recovery regimes produce a sizable portion of waste water brine. This brine is highly toxic and water recovery is poor: a highly wasteful proposition. With new biological techniques that do not require waste water chemical pretreatment, the resulting brine would be chromium-free and nitrate rich which can allow possible fertilizer recovery for future plant systems. Using a system of ion exchange resins we can remove hardness, sulfate, phosphate and nitrate from these brines to leave only sodium and potassium chloride. At this point modern chlor-alkali cells can be utilized to produce a low salt stream as well as an acid and base stream. The first stream can be used to gain higher water recovery through recycle to the water separation stage while the last two streams can be used to regenerate the ion exchange beds used here, as well as other ion exchange beds in the ISS. Conveniently these waste products from ion exchange regeneration would be suitable as plant fertilizer. In this report we go over the performance of state of the art resins designed for high selectivity of target ions under brine conditions. Using ersatz ISS waste water we can evaluate the performance of specific resins and calculate mass balances to determine resin effectiveness and process viability. If this system is feasible then we will be one step closer to closed loop environmental control and life support systems (ECLSS) for current or future applications.

  13. High-capacity, selective solid sequestrants for innovative chemical separation: Inorganic ion exchange approach

    International Nuclear Information System (INIS)

    Bray, L.

    1995-01-01

    The approach of this task is to develop high-capacity, selective solid inorganic ion exchangers for the recovery of cesium and strontium from nuclear alkaline and acid wastes. To achieve this goal, Pacific Northwest Laboratories (PNL) is collaborating with industry and university participants to develop high capacity, selective, solid ion exchangers for the removal of specific contaminants from nuclear waste streams

  14. Chemical characterization of individual microparticles using an ion trap: real-time chemical analysis of aerosol particles

    International Nuclear Information System (INIS)

    Yang, Mo; Whitten, W.B.; Reilly, P.T.A.; Gieray, R.; Ramsey, J.M.

    1996-01-01

    This paper describes initial experiments to perform laser ablation mass spectrometry in real time on airborne microparticles. The microparticles are sampled directly from the air by a particle inlet system into the vacuum chamber of a mass spectrometer. An incoming particle is detected as it passes through two CW laser beams and a pulsed laser is triggered to intercept the particle for laser ablation/ionization in the mass spectrometer. The initial studies were made with an existing ion trap mass spectrometer with the particle sampling occurring at the center of the trap electrodes. Performance of the inlet system, particle detection, and preliminary results are described

  15. PVP-coated silver nanoparticles and silver ions induce reactive oxygen species, apoptosis and necrosis in THP-1 monocytes

    DEFF Research Database (Denmark)

    Foldbjerg, Rasmus; Olesen, Ping Liu; Hougaard, Mads

    2009-01-01

    , both Ag NPs and Ag+ were shown to induce apoptosis and necrosis in THP-1 cells depending on dose and exposure time. Furthermore, the presence of apoptosis could be confirmed by the TUNEL method. A number of studies have implicated the production of reactive oxygen species (ROS) in cytotoxicity mediated...... the effect of well characterized, PVP-coated Ag NPs (69 nm ± 3 nm) and Ag+ in a human monocytic cell line (THP-1). Characterization of the Ag NPs was conducted in both stock suspension and cell media with or without serum and antibiotics. By using the flowcytometric annexin V/propidium iodide (PI) assay...... by NPs. We used the fluorogenic probe, 2′,7′-dichlorofluorescein to assess the levels of intracellular ROS during exposure to Ag NPs and Ag+. A drastic increase in ROS levels could be detected after 6–24 h suggesting that oxidative stress is an important mediator of cytotoxicity caused by Ag NPs and Ag+....

  16. Chemical analysis of reactive species and antimicrobial activity of/nwater treated by nanosecond pulsed DBD air plasma

    Czech Academy of Sciences Publication Activity Database

    Laurita, R.; Barbieri, D.; Gherardi, M.; Colombo, V.; Lukeš, Petr

    2015-01-01

    Roč. 3, č. 2 (2015), s. 53-61 ISSN 2212-8166 R&D Projects: GA MŠk(CZ) LD14080 Grant - others:European Cooperation in Science and Technology(XE) COST TD1208 Institutional support: RVO:61389021 Keywords : Dielectric barrier discharge * Plasma activated water * Reactive species * Peroxynitrite * Phenol degradation * Candida albicans * Staphylococcus aureus * Antimicrobial activity * Nosocomial infections Subject RIV: BL - Plasma and Gas Discharge Physics http://www.sciencedirect.com/science/article/pii/S2212816615300081

  17. Transformation of alpha-tocopherol (vitamin E) and related chromanol model compounds into their phenoxonium ions by chemical oxidation with the nitrosonium cation.

    Science.gov (United States)

    Lee, Stephen B; Lin, Ching Yeh; Gill, Peter M W; Webster, Richard D

    2005-12-09

    [reaction: see text] Alpha-tocopherol (alpha-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO+ SbF6(-) in CH3CN at 233 K to form phenoxonium cations (alpha-TO+ SbF6(-)) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, 1H and 13C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.

  18. Generation and Role of Reactive Oxygen and Nitrogen Species Induced by Plasma, Lasers, Chemical Agents, and Other Systems in Dentistry

    Science.gov (United States)

    Jha, Nayansi; Ryu, Jae Jun

    2017-01-01

    The generation of reactive oxygen and nitrogen species (RONS) has been found to occur during inflammatory procedures, during cell ischemia, and in various crucial developmental processes such as cell differentiation and along cell signaling pathways. The most common sources of intracellular RONS are the mitochondrial electron transport system, NADH oxidase, and cytochrome P450. In this review, we analyzed the extracellular and intracellular sources of reactive species, their cell signaling pathways, the mechanisms of action, and their positive and negative effects in the dental field. In dentistry, ROS can be found—in lasers, photosensitizers, bleaching agents, cold plasma, and even resin cements, all of which contribute to the generation and prevalence of ROS. Nonthermal plasma has been used as a source of ROS for biomedical applications and has the potential for use with dental stem cells as well. There are different types of dental stem cells, but their therapeutic use remains largely untapped, with the focus currently on only periodontal ligament stem cells. More research is necessary in this area, including studies about ROS mechanisms with dental cells, along with the utilization of reactive species in redox medicine. Such studies will help to provide successful treatment modalities for various diseases. PMID:29204250

  19. Host-cell reactivation of UV-irradiated and chemically-treated herpes simplex virus-1 by xeroderma pigmentosum, xp heterozygotes and normal skin fibroblasts

    International Nuclear Information System (INIS)

    Selsky, C.A.

    1978-01-01

    The host-cell reactivation of UV-irradiated and N-acetoxy-2-acetylamino-fluorene-treated herpes simplex virus type 1 strain MP was studied in normal and xeroderma pigmentosum human skin fibroblasts. Virus treated with either agent demonstrated lower survival in XP cells from complementation groups A, B, C and D than in normal fibroblasts. The relative reactivation ability of XP cells from the different genetic complementation groups was found to be the same for both irradiated and chemically treated virus. In addition, the inactivation kinetics for virus treated with either agent in the XP variant were comparable to that seen in normal skin fibroblasts. The addition of 2 or 4 mmoles caffeine to the post-infection assay medium had no effect on the inactivation kinetics of virus treated by either agent in the XP variant or in XP cells from the different genetic complementation groups. Treatment of the virus with nitrogen mustard resulted in equivalent survival in normal and XP genetic complementation group D cells. No apparent defect was observed in the ability of XP heterozygous skin fibroblasts to repair virus damaged with up to 100 μg N-acetoxy-2-acetylaminofluorene per ml. These findings indicate that the repair of UV-irradiated and N-acetoxy-2-acetylaminofluorene-treated virus is accomplished by the same pathway or different pathways sharing a common intermediate step and that the excision defect of XP cells plays little if any role in the reactivation of nitrogen mustard treated virus. (Auth.)

  20. Oral Administration of the Japanese Traditional Medicine Keishibukuryogan-ka-yokuinin Decreases Reactive Oxygen Metabolites in Rat Plasma: Identification of Chemical Constituents Contributing to Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Yosuke Matsubara

    2017-02-01

    Full Text Available Insufficient detoxification and/or overproduction of reactive oxygen species (ROS induce cellular and tissue damage, and generated reactive oxygen metabolites become exacerbating factors of dermatitis. Keishibukuryogan-ka-yokuinin (KBGY is a traditional Japanese medicine prescribed to treat dermatitis such as acne vulgaris. Our aim was to verify the antioxidant properties of KBGY, and identify its active constituents by blood pharmacokinetic techniques. Chemical constituents were quantified in extracts of KBGY, crude components, and the plasma of rats treated with a single oral administration of KBGY. Twenty-three KBGY compounds were detected in plasma, including gallic acid, prunasin, paeoniflorin, and azelaic acid, which have been reported to be effective for inflammation. KBGY decreased level of the diacron-reactive oxygen metabolites (d-ROMs in plasma. ROS-scavenging and lipid hydroperoxide (LPO generation assays revealed that gallic acid, 3-O-methylgallic acid, (+-catechin, and lariciresinol possess strong antioxidant activities. Gallic acid was active at a similar concentration to the maximum plasma concentration, therefore, our findings indicate that gallic acid is an important active constituent contributing to the antioxidant effects of KBGY. KBGY and its active constituents may improve redox imbalances induced by oxidative stress as an optional treatment for skin diseases.

  1. Investigation of hydrogen content in chemically delithiated lithium-ion battery cathodes using prompt gamma activation analysis

    International Nuclear Information System (INIS)

    Aghara, S.K.; Alvarez II, E.; Venkatraman, S.; Manthiram, A.

    2005-01-01

    Lithium-ion batteries are widely used as a power source for portable electronic devices. Currently, only 50-70% of the theoretical capacity of the layered oxide cathode (positive electrode) materials could be reversibly used. The reason for this limitation is not fully understood in the literature. Recent structural and chemical characterizations of chemically delithiated (charged) cathodes suggest that loss of oxygen from the lattice may play a role in this regard. However, during the chemical delithiation process any proton inserted from the solvent could adversely affect the oxygen content analysis data. The challenge in addressing this issue is to detect and determine precisely the proton content in the chemically delithiated samples. The prompt gamma-ray activation analysis (PGAA) facility at the Nuclear Engineering Teaching Laboratory (NETL) is used to determine the proton content in the layered oxide cathode LiNi 0.5 Mn 0.5 O 2 before and after chemical delithiation. The data are compared with those obtained with Fourier transform infrared (FTIR) spectroscopy, which can provide mainly qualitative analysis. The technique has proved to be promising for these compounds and will be applied to characterize several other chemically delithiated Li 1-x Co 1-y M y O 2 (M = Cr, Mn, Fe, Ni, Cu, Mg, and Al) cathodes. (author)

  2. Mixed ion-exchanger chemically modified carbon paste ion-selective electrodes for determination of triprolidine hydrochloride

    Directory of Open Access Journals (Sweden)

    Yousry M. Issa

    2010-01-01

    Full Text Available Triprolidine hydrochloride (TpCl ion-selective carbon paste electrodes were constructed using Tp-TPB/Tp-CoN and Tp-TPB/Tp-PTA as ion-exchangers. The two electrodes revealed Nernstian responses with slopes of 58.4 and 58.1 mV decade−1 at 25 °C in the ranges 6 × 10−6–1 × 10−2 and 2 × 10−5–1 × 10−2 M for Tp-TPB/Tp-CoN and Tp-TPB/Tp-PTA, respectively. The potentials of these electrodes were independent of pH in the ranges of 2.5–7.0 and 4.5–7.0, and detection limits were 6 × 10−6 and 1 × 10−5 M for Tp-TPB/Tp-CoN and Tp-TPB/Tp-PTA, respectively. The electrodes showed a very good selectivity for TpCl with respect to a large number of inorganic cations and compounds. The standard addition, potentiometric titration methods and FIA were applied to the determination of TpCl in pure solutions and pharmaceutical preparations. The results obtained were in close agreement with those found by the official method. The mean recovery values were 100.91% and 97.92% with low coefficient of variation values of 0.94%, and 0.56% in pure solutions, 99.82% and 98.53% with coefficient of variation values of 2.20%, and 0.73% for Actifed tablet and Actifed syrup, respectively, using the Tp-TPB/Tp-CoN electrode, and 98.85%, and 99.18% with coefficient of variation values of 0.48% and 0.85% for Actifed tablet and Actifed syrup, respectively, using the Tp-TPB/Tp-PTA electrode.

  3. Physico-chemical changes in heavy ions irradiated polymer foils by differential scanning calorimetry

    International Nuclear Information System (INIS)

    Ciesla, K.; Trautmann, Ch.; Vansant, E.F.

    1994-01-01

    The sample of commercial PETP (Hostaphan) and very heavy ions irradiated products were investigated by differential scanning calorimetry in nitrogen flow. Irradiation were performed with Dy ions of 13 MeV/u with fluences 5 x 10 10 ions/cm 2 . Differences were observed in melting behaviour of unirradiated and irradiated foils. The influence of irradiation conditions on the results was noticed. Moreover the samples of polyimide (Kapton) and polycarbonate (Macrofol) irradiated in similar conditions were examined by DSC. The DSC traces have been compared with those of unirradiated reference samples. (author). 8 refs, 5 figs

  4. Inorganic ion exchangers and adsorbents for chemical processing in the nuclear fuel cycle

    International Nuclear Information System (INIS)

    1985-07-01

    The application of inorganic ion exchangers and adsorbents to both waste treatment and the recovery of fission products and actinides were of primary concern at this meeting. The meeting covered the two major fields of fundamental studies and industrial applications

  5. Coupled chemical reactions in dynamic nanometric confinement: Ag2O membrane formation during ion track etching

    Czech Academy of Sciences Publication Activity Database

    Hernandez, G. M.; Cruz, S. A.; Quintero, R.; Arellano, H. G.; Fink, Dietmar; Alfonta, L.; Mandabi, Y.; Kiv, A.; Vacík, Jiří

    2013-01-01

    Roč. 168, č. 9 (2013), s. 675-695 ISSN 1042-0150 Institutional support: RVO:61389005 Keywords : track * polymers * etching * chemistry * ions * nanostructure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.603, year: 2013

  6. Compact Chemical Monitor for Silver Ions in Spacecraft Water Systems, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — NASA has identified silver ions as the best candidate biocide for use in the potable water system on next-generation spacecraft. Though significant work has been...

  7. Synthesis and performance of cerium oxide as anode materials for lithium ion batteries by a chemical precipitation method

    International Nuclear Information System (INIS)

    Liu, Haowen; Le, Qi

    2016-01-01

    In this present work, chemical precipitation method was employed for preparing cerium oxide. XRD, SEM, TEM, TGA/DTA and BET were used to investigate the structure, shape and formation mechanism, respectively. No impurities were detected. It was found that alcohol had obvious effection on the growth of the final sample. The shape of the precursor was retained after calcined at 500 °C. This result led to the possibility of an easy scale up to a commercial process. EIS and charge–discharge tests were carried out by using the as-prepared CeO_2 as an anode material for lithium ion batteries. Specially, the initial discharge specific capacity of the rhombus CeO_2 was about 529 mAh g"−"1 and stabilized reversibly at about 374 mAh g"−"1 after 50 cycles. It showed a promising usage as anode materials in lithium ion battery. - Highlights: • Chemical precipitation method was employed for the synthesis of cerium oxide. • Alcohol has obvious effection on the growth of the final sample. • The rhombus CeO_2 showed the better electrochemical properties as anode of lithium ion batteries.

  8. Synthesis and performance of cerium oxide as anode materials for lithium ion batteries by a chemical precipitation method

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haowen, E-mail: liuhwchem@hotmail.com; Le, Qi

    2016-06-05

    In this present work, chemical precipitation method was employed for preparing cerium oxide. XRD, SEM, TEM, TGA/DTA and BET were used to investigate the structure, shape and formation mechanism, respectively. No impurities were detected. It was found that alcohol had obvious effection on the growth of the final sample. The shape of the precursor was retained after calcined at 500 °C. This result led to the possibility of an easy scale up to a commercial process. EIS and charge–discharge tests were carried out by using the as-prepared CeO{sub 2} as an anode material for lithium ion batteries. Specially, the initial discharge specific capacity of the rhombus CeO{sub 2} was about 529 mAh g{sup −1} and stabilized reversibly at about 374 mAh g{sup −1} after 50 cycles. It showed a promising usage as anode materials in lithium ion battery. - Highlights: • Chemical precipitation method was employed for the synthesis of cerium oxide. • Alcohol has obvious effection on the growth of the final sample. • The rhombus CeO{sub 2} showed the better electrochemical properties as anode of lithium ion batteries.

  9. Enhanced signal generation for use in the analysis of synthetic pyrethroids using chemical ionization tandem quadrupole ion trap mass spectrometry.

    Science.gov (United States)

    Sichilongo, Kwenga

    2004-12-01

    Synthetic pyrethroids fragment extensively under electron ionization (EI) conditions to give low mass ions, most of them with the same m/z ratios. This fragmentation is primarily due to the labile ester linkage found in these compounds. In this research we established the best gas chromatography (GC) conditions in the EI mode that served as a benchmark in the development of a chemical ionization (CI) protocol for ten selected synthetic pyrethroids. Based on proton affinity data, several reagent gases were evaluated in the positive CI ionization mode. Methanol was found to produce higher average ion counts relative to the other gases evaluated, which led to the development of an optimized method consisting of selective ejection chemical ionization (SECI) and MS/MS. Standard stainless steel ion trap electrodes produced significant degradation of chromatographic performance on late eluting compounds, which was attributed to electrode surface chemistry. A dramatic improvement in signal-to-noise (S/N) ratios was observed when the chromatographically inert Silcosteel coated electrodes were used. The resulting method, that has significant S/N ratio improvements resulting from a combination of septum programmable injections (SPI), optimized CI and inert Silcosteel-coated electrodes, was used to determine instrument detection limits.

  10. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    International Nuclear Information System (INIS)

    Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Viggiano, Albert A.; Pedder, Randall E.; Taormina, Christopher R.

    2015-01-01

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H 3 O + , but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re + with O 2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re 2 2+ is found to charge transfer with O 2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba + , which is reacted with N 2 O to create BaO + , and we find a rate constant that agrees with the literature

  11. Formulation of chemically reactive foams for the dissolution of oxides polluting the secondary circuits of steam generators

    International Nuclear Information System (INIS)

    Provens, Helene

    1999-01-01

    The fouling of the Steam Generators (SG) secondary circuits, due to oxides deposits like magnetite (Fe 3 O 4 ), induces the degradation of the internal SG equipment, the reduction of the plant power, implying to clean these circuits. This operation made in liquid phase generates an important volume of effluents with an expensive cost of treatment. The use of a reactive foam allows the reduction of this volume by ten. Among the reactive tested, oxalic acid is the most efficient to dissolve a magnetite quantity of 10 g.l -1 , at ambient temperature for 24 hours, as imposed by the industrial wishes. The dissolution is not complete in our experimental conditions and is a complex reaction of autocatalytic type, composed of an acid attack, a reductive step, both followed by a slow diffusion. The surfactants generating the foam, which transport the reactive, are adsorbed on the magnetite but this affects weakly the dissolution. Its effectiveness is evaluated varying the experimental conditions. The wetting properties and the stability of the foam induce erosion and undissolved particles transport capacities, during its circulation into the SG. These particles trapped in the inter-bubble liquid films or carried by the piston effect of the foam bed, can be recovered on filters placed out of the SG. To quantify the transport, the influence of different parameters is studied: the more stable the foam is, the more important the transport is. Innocuousness tests showed that oxalic acid was not harmful for constitutive SG materials, either they were isolated or coupled. The cleaning by oxalic acid causes ferrous oxalates precipitation, representing 10 to 15 pc of the total iron quantity depending on the sample. A rinsing out with a foam containing 1 pc oxalic acid and 5 pc hydrogen peroxide allows the dissolution of these precipitates without corrosion problems. (author) [fr

  12. Heavy metal incorporated helium ion active hybrid non-chemically amplified resists: Nano-patterning with low line edge roughness

    Directory of Open Access Journals (Sweden)

    Pulikanti Guruprasad Reddy

    2017-08-01

    Full Text Available Helium (He ion lithography is being considered as one of the most promising and emerging technology for the manufacturing of next generation integrated circuits (ICs at nanolevel. However, He-ion active resists are rarely reported. In this context, we are introducing a new non-chemically amplified hybrid resist (n-CAR, MAPDSA-MAPDST, for high resolution He-ion beam lithography (HBL applications. In the resist architecture, 2.15 % antimony is incorporated as heavy metal in the form of antimonate. This newly developed resists has successfully used for patterning 20 nm negative tone features at a dose of 60 μC/cm2. The resist offered very low line edge roughness (1.27±0.31 nm for 20 nm line features. To our knowledge, this is the first He-ion active hybrid resist for nanopatterning. The contrast (γ and sensitivity (E0 of this resist were calculated from the contrast curve as 0.73 and 7.2 μC/cm2, respectively.

  13. Heavy metal incorporated helium ion active hybrid non-chemically amplified resists: Nano-patterning with low line edge roughness

    Science.gov (United States)

    Reddy, Pulikanti Guruprasad; Thakur, Neha; Lee, Chien-Lin; Chien, Sheng-Wei; Pradeep, Chullikkattil P.; Ghosh, Subrata; Tsai, Kuen-Yu; Gonsalves, Kenneth E.

    2017-08-01

    Helium (He) ion lithography is being considered as one of the most promising and emerging technology for the manufacturing of next generation integrated circuits (ICs) at nanolevel. However, He-ion active resists are rarely reported. In this context, we are introducing a new non-chemically amplified hybrid resist (n-CAR), MAPDSA-MAPDST, for high resolution He-ion beam lithography (HBL) applications. In the resist architecture, 2.15 % antimony is incorporated as heavy metal in the form of antimonate. This newly developed resists has successfully used for patterning 20 nm negative tone features at a dose of 60 μC/cm2. The resist offered very low line edge roughness (1.27±0.31 nm) for 20 nm line features. To our knowledge, this is the first He-ion active hybrid resist for nanopatterning. The contrast (γ) and sensitivity (E0) of this resist were calculated from the contrast curve as 0.73 and 7.2 μC/cm2, respectively.

  14. Influence of both ion bombardment and chemical treatment processes on the electrical conductivity of PVC/poly aniline composites

    International Nuclear Information System (INIS)

    Gad, E.A.M.; Ashour, A.H.; Abdel-Hamid, H.M.; Sayed, W.M.

    1999-01-01

    In this article the changes in the electrical conductivity of PVC/poly aniline composites, as temperature consecutively increases, have been measured. The measurement were taken with correspondence to a control series of the composites under two processes:A. Composite samples bombarded with Ar + ions with fluence 2.44 x 10 13 beam ions /cm 2 ., sec 4 of 4 ke V beam energy where argon atoms can induce defects in the surface layer take place. Composite samples treated chemically with concentrated H 2 SO 4 as dopant which reacts with nitrogen atom in aniline. The measurements were also, done with the composites as the ratio of poly(aniline) stepped upward

  15. Luminescent chemical waves in the Cu(II)-catalyzed oscillatory oxidation of SCN- ions with hydrogen peroxide.

    Science.gov (United States)

    Pekala, Katarzyna; Jurczakowski, Rafał; Lewera, Adam; Orlik, Marek

    2007-05-10

    The oscillatory oxidation of thiocyanate ions with hydrogen peroxide, catalyzed by Cu2+ ions in alkaline media, was so far observed as occurring simultaneously in the entire space of the batch or flow reactor. We performed this reaction for the first time in the thin-layer reactor and observed the spatiotemporal course of the above process, in the presence of luminol as the chemiluminescent indicator. A series of luminescent patterns periodically starting from the random reaction center and spreading throughout the entire solution layer was reported. For a batch-stirred system, the bursts of luminescence were found to correlate with the steep decreases of the oscillating Pt electrode potential. These novel results open possibilities for further experimental and theoretical investigations of those spatiotemporal patterns, including studies of the mechanism of this chemically complex process.

  16. 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

  17. Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2017-01-15

    Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

  18. Removal of heavy metal ions by magnetic chitosan nanoparticles prepared continuously via high-gravity reactive precipitation method.

    Science.gov (United States)

    Fan, Hong-Lei; Zhou, Shao-Feng; Jiao, Wei-Zhou; Qi, Gui-Sheng; Liu, You-Zhi

    2017-10-15

    This study aimed to provide a continuous method for the preparation of magnetic Fe 3 O 4 /Chitosan nanoparticles (Fe 3 O 4 /CS NPs) that can be applied to efficient removal of heavy metal ions from aqueous solution. Using a novel impinging stream-rotating packed bed, the continuous preparation of Fe 3 O 4 /CS NPs reached a theoretical production rate of 3.43kg/h. The as-prepared Fe 3 O 4 /CS NPs were quasi-spherical with average diameter of about 18nm and saturation magnetization of 33.5emu/g. Owing to the strong metal chelating ability of chitosan, the Fe 3 O 4 /CS NPs exhibited better adsorption capacity and faster adsorption rates for Pb(II) and Cd(II) than those of pure Fe 3 O 4 . The maximum adsorption capacities of Fe 3 O 4 /CS NPs for Pb(II) and Cd(II) were 79.24 and 36.42mgg -1 , respectively. In addition, the Fe 3 O 4 /CS NPs shown excellent reusability after five adsorption-desorption cycles. All the above results provided a potential method for continuously preparing recyclable adsorbent with a wide prospect of application in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. A chemically selective laser ion source for the on-line isotope separation

    International Nuclear Information System (INIS)

    Scheerer, F.

    1993-03-01

    In this thesis a laser ion source is presented. In a hot chamber the atoms of the elements to be studied are resonantly by light of pulsed dye lasers, which are pumped by pulsed copper-vapor lasers with extremely high pulse repetition rate (ν rep ∼ 10 kHz), stepwise excited and ionized. By the storage of the atoms in a hot chamber and the high pulse repetition rate of the copper-vapor lasers beyond the required high efficiency (ε ∼ 10%) can be reached. First preparing measurements were performed at the off-line separator at CERN with the rare earth elements ytterbium and thulium. Starting from the results of these measurements further tests of the laser ion source were performed at the on-line separator with in a thick tantalum target produced neutron-deficient ytterbium isotopes. Under application of a time-of-flight mass spectrometer in Mainz an efficient excitation scheme on the resonance ionization of tin was found. This excitation scheme is condition for an experiment at the GSI for the production of the extremely neutron-deficient, short-lived nucleus 102 Sn. In the summer 1993 is as first application of the newly developed laser ion source at the PSB-ISOLDE at CERN an astrophysically relevant experiment for the nuclear spectroscopy of the neutron-rich silver isotopes 124-129 Ag is planned. This experiment can because of the lacking selectivity of conventional ion sources only be performed by means of the here presented laser ion source. The laser ion source shall at the PSB-ISOLDE 1993 also be applied for the selective ionization of manganese. (orig./HSI) [de

  20. Investigation of chemical changes in uranium oxyfluoride particles using secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Kips, R.S.; Kristo, M.J.

    2009-01-01

    Understanding how environmental conditions may affect sample composition is critical to the interpretation of laboratory analyses from environmental sampling. We prepared a set of UO 2 F 2 particle samples from the hydrolysis of UF 6 and stored these samples in environmental chambers at different temperature, humidity and lighting conditions. The NanoSIMS ion microprobe was used to measure the UF + /U + secondary ion ratio of individual particles. Monitoring variations in this ratio may provide insights on changes in particle composition over time and in response to environmental exposure. This report presents the baseline measurements carried out on freshly-prepared particle samples to determine the initial amount of fluorine. (author)

  1. Role of ion chromatography in the chemical characterization of PFBR MOX fuel

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Das, D.K.; Prakash, Amrit; Behere, P.G.; Afzal, Mohd

    2012-01-01

    Ion chromatography (IC) is multi-element technique with the feasibility of determination of metallic as well as non metallic impurities on a single instrument. IC has been used for various analytical purposes in nuclear industry. lt has advantages of low capital investment, small sample size, less radioactive waste generation, comparable precision to spectroscopic techniques and ease of fume hood/glove box adaptation. Present paper describes the determination of trace metallic (alkali, alkaline earth, transition and lanthanide metal ions) and non metallic impurities in PFBR MOX fuel

  2. The most reactive third-row transition metal: Guided ion beam and theoretical studies of the activation of methane by Ir+

    Science.gov (United States)

    Li, Feng-Xia; Zhang, Xiao-Guang; Armentrout, P. B.

    2006-09-01

    The potential energy surface for activation of methane by the third-row transition metal cation, Ir+, is studied experimentally by examining the kinetic energy dependence of reactions of Ir+ with methane, IrCH2+ with H2 and D2, and collision-induced dissociation of IrCH2+ with Xe using guided ion beam tandem mass spectrometry. A flow tube ion source produces Ir+ in its electronic ground state term and primarily in the ground spin-orbit level. We find that dehydrogenation to form IrCH2+ + H2 is exothermic, efficient, and the only process observed at low energies for reaction of Ir+ with methane, whereas IrH+ dominates the product spectrum at higher energies. We also observe the IrH2+ product, which provides evidence that methane activation proceeds via a dihydride (H)2IrCH2+ intermediate. The kinetic energy dependences of the cross sections for several endothermic reactions are analyzed to give 0 K bond dissociation energies (in eV) of D0(Ir+-2H) > 5.09 +/- 0.07, D0(Ir+-C) = 6.59 +/- 0.05, D0(Ir+-CH) = 6.91 +/- 0.23, and D0(Ir+-CH3) = 3.25 +/- 0.18. D0(Ir+-CH2) = 4.92 +/- 0.03 eV is determined by measuring the forward and reverse reaction rates for Ir++CH4[right harpoon over left]IrCH2++H2 at thermal energy. Ab initio calculations at the B3LYP/HW+/6-311++G(3df,3p) level performed here show reasonable agreement with the experimental bond energies and with the few previous experimental and theoretical values available. Theory also provides the electronic structures of the product species as well as intermediates and transition states along the reactive potential energy surfaces. We also compare this third-row transition metal system with the first-row and second-row congeners, Co+ and Rh+. Differences in reactivity and mechanisms can be explained by the lanthanide contraction and relativistic effects that alter the relative size of the valence s and d orbitals.

  3. Influence of substrate pre-treatments by Xe{sup +} ion bombardment and plasma nitriding on the behavior of TiN coatings deposited by plasma reactive sputtering on 100Cr6 steel

    Energy Technology Data Exchange (ETDEWEB)

    Vales, S., E-mail: sandra.vales@usp.br [Universidade de São Paulo (USP), Escola de Engenharia de São Carlos, Av. Trabalhador São Carlense 400, São Carlos, SP CEP 13566-590 (Brazil); Brito, P., E-mail: ppbrito@gmail.com [Pontifícia Universidade Católica de Minas Gerais (PUC-MG), Av. Dom José Gaspar 500, 30535-901 Belo Horizonte, MG (Brazil); Pineda, F.A.G., E-mail: pipe8219@gmail.com [Universidade de São Paulo (USP), Escola de Engenharia de São Carlos, Av. Trabalhador São Carlense 400, São Carlos, SP CEP 13566-590 (Brazil); Ochoa, E.A., E-mail: abigail_ochoa@hotmail.com [Universidade Estadual de Campinas (UNICAMP), Campus Universitário Zeferino Vaz, Barão Geraldo, Campinas, SP CEP 13083-970 (Brazil); Droppa, R., E-mail: roosevelt.droppa@ufabc.edu.br [Universidade Federal do ABC (UFABC), Av. dos Estados, 5001, Santo André, SP CEP 09210-580 (Brazil); Garcia, J., E-mail: jose.garcia@sandvik.com [Sandvik Coromant R& D, Lerkrogsvägen 19, SE-12680, Stockholm (Sweden); Morales, M., E-mail: monieriz@gmail.com [Universidade Estadual de Campinas (UNICAMP), Campus Universitário Zeferino Vaz, Barão Geraldo, Campinas, SP CEP 13083-970 (Brazil); Alvarez, F., E-mail: alvarez@ifi.unicamp.br [Universidade Estadual de Campinas (UNICAMP), Campus Universitário Zeferino Vaz, Barão Geraldo, Campinas, SP CEP 13083-970 (Brazil); and others

    2016-07-01

    In this paper the influence of pre-treating a 100Cr6 steel surface by Xe{sup +} ion bombardment and plasma nitriding at low temperature (380 °C) on the roughness, wear resistance and residual stresses of thin TiN coatings deposited by reactive IBAD was investigated. The Xe{sup +} ion bombardment was carried out using a 1.0 keV kinetic energy by a broad ion beam assistance deposition (IBAD, Kaufman cell). The results showed that in the studied experimental conditions the ion bombardment intensifies nitrogen diffusion by creating lattice imperfections, stress, and increasing roughness. In case of the combined pre-treatment with Xe{sup +} ion bombardment and subsequent plasma nitriding, the samples evolved relatively high average roughness and the wear volume increased in comparison to the substrates exposed to only nitriding or ion bombardment. - Highlights: • Effect of Xe ion bombardment and plasma nitriding on TiN coatings was investigated. • Xe ion bombardment with 1.0 KeV increases nitrogen retention in plasma nitriding. • 1.0 KeV ion impact energy causes sputtering, thus increasing surface roughness. • TiN coating wear is minimum after plasma nitriding due to lowest roughness.

  4. Engineering of the chemical reactivity of the Ti/HfO₂ interface for RRAM: experiment and theory.

    Science.gov (United States)

    Calka, Pauline; Sowinska, Malgorzata; Bertaud, Thomas; Walczyk, Damian; Dabrowski, Jarek; Zaumseil, Peter; Walczyk, Christian; Gloskovskii, Andrei; Cartoixà, Xavier; Suñé, Jordi; Schroeder, Thomas

    2014-04-09

    The Ti/HfO2 interface plays a major role for resistance switching performances. However, clear interface engineering strategies to achieve reliable and reproducible switching have been poorly investigated. For this purpose, we present a comprehensive study of the Ti/HfO2 interface by a combined experimental-theoretical approach. Based on the use of oxygen-isotope marked Hf*O2, the oxygen scavenging capability of the Ti layer is clearly proven. More importantly, in line with ab initio theory, the combined HAXPES-Tof-SIMS study of the thin films deposited by MBE clearly establishes a strong impact of the HfO2 thin film morphology on the Ti/HfO2 interface reactivity. Low-temperature deposition is thus seen as a RRAM processing compatible way to establish the critical amount of oxygen vacancies to achieve reproducible and reliable resistance switching performances.

  5. Probing the reactivity of nucleophile residues in human 2,3-diphosphoglycerate/deoxy-hemoglobin complex by aspecific chemical modifications.

    Science.gov (United States)

    Scaloni, A; Ferranti, P; De Simone, G; Mamone, G; Sannolo, N; Malorni, A

    1999-06-11

    The use of aspecific methylation reaction in combination with MS procedures has been employed for the characterization of the nucleophilic residues present on the molecular surface of the human 2,3-diphosphoglycerate/deoxy-hemoglobin complex. In particular, direct molecular weight determinations by ESMS allowed to control the reaction conditions, limiting the number of methyl groups introduced in the modified globin chains. A combined LCESMS-Edman degradation approach for the analysis of the tryptic peptide mixtures yielded to the exact identification of methylation sites together with the quantitative estimation of their degree of modification. The reactivities observed were directly correlated with the pKa and the relative surface accessibility of the nucleophilic residues, calculated from the X-ray crystallographic structure of the protein. The results here described indicate that this methodology can be efficiently used in aspecific modification experiments directed to the molecular characterization of the surface topology in proteins and protein complexes.

  6. Chemical Potentials of Quarks Extracted from Particle Transverse Momentum Distributions in Heavy Ion Collisions at RHIC Energies

    International Nuclear Information System (INIS)

    Zhao, Hong; Liu, Fu-Hu

    2014-01-01

    In the framework of a multisource thermal model, the transverse momentum distributions of charged particles produced in nucleus-nucleus (A-A) and deuteron-nucleus (d-A) collisions at relativistic heavy ion collider (RHIC) energies are investigated by a two-component revised Boltzmann distribution. The calculated results are in agreement with the PHENIX experimental data. It is found that the source temperature increases obviously with increase of the particle mass and incident energy, but it does not show an obvious change with the collision centrality. Then, the values of chemical potentials for up, down, and strange quarks can be obtained from the antiparticle to particle yield ratios in a wide transverse momentum range. The relationship between the chemical potentials of quarks and the transverse momentum with different centralities is investigated, too

  7. Investigating the Chemical Reactivity for Hydrogen in Siliciclastic Sediments: two Work Packages of the H2STORE Project

    Science.gov (United States)

    De Lucia, M.; Pilz, P.

    2014-12-01

    The H2STORE ("Hydrogen to Store") collaborative project, funded by the German government, investigates the feasibility of industrial-scale hydrogen storage from excess wind energy in siliciclastic depleted gas and oil reservoirs or suitable saline aquifers. In particular, two work packages (geochemical experiments and modelling) hosted at the German Research Centre for Geosciences (GFZ) focus on the possible impact of hydrogen on formation fluids and on the mineralogical, geochemical and petrophysical properties of reservoirs and caprocks. Laboratory experiments expose core samples from several potential reservoirs to pure hydrogen or hydrogen mixtures under site-specific conditions (temperatures up to 200 °C and pressure up to 300 bar). The resulting qualitative and, whereas possible, quantitative data are expected to ameliorate the precision of predictive geochemical and reactive transport modelling, which is also performed within the project. The combination of experiments and models will improve the knowledge about: (1) solubility model and mixing rule for of hydrogen and its gas mixtures in high saline formation fluids; (2) hydrogen reactivity in a broad spectrum of P-T conditions; (3) thermodynamics and kinetics of mineral dissolution or precipitation reactions and redox processes. It is known that under specific P-T conditions reactions between hydrogen and anorganic rock components such as carbonates can occur. However these conditions have never been precisely defined to date. A precise estimation of the hydrogen impact on reservoir behavior of different siliciclastic rock types is crucial for site selection and optimization of storage depth. Enhancing the overall understanding of such systems will benefit the operational reliability, the ecological tolerance, and the economic efficiency of future energy storing plants, crucial aspects for public acceptance and for industrial investors.

  8. Ion mobility spectrometric analysis of vaporous chemical warfare agents by the instrument with corona discharge ionization ammonia dopant ambient temperature operation.

    Science.gov (United States)

    Satoh, Takafumi; Kishi, Shintaro; Nagashima, Hisayuki; Tachikawa, Masumi; Kanamori-Kataoka, Mieko; Nakagawa, Takao; Kitagawa, Nobuyoshi; Tokita, Kenichi; Yamamoto, Soichiro; Seto, Yasuo

    2015-03-20

    The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman

  9. Adsorption of ions on hematite (α-Fe2O3) : a colloid-chemical study

    NARCIS (Netherlands)

    Breeuwsma, A.

    1973-01-01

    This study is primarily intended to provide a better understanding of the adsorption of ions on hematite (α-Fe 2 O 3 ). In addition, due attention is given to the relation between the ionic adsorption and the colloidal stability of hematite sols.

    Chapter 1. is concerned

  10. Chemical recycling of cell phone Li-ion batteries: Application in environmental remediation.

    Science.gov (United States)

    Gonçalves, Mariana C Abreu; Garcia, Eric M; Taroco, Hosane A; Gorgulho, Honória F; Melo, Júlio O F; Silva, Rafael R A; Souza, Amauri G

    2015-06-01

    This paper presents, for the first time, the recycling and use of spent Li-ion battery cathode tape as a catalyst in the degradation of an organic dye. In our proposal, two major environmental problems can be solved: the secure disposal of cell phone batteries and the treatment of effluents with potentially toxic organic dyes. The spent Li-ion battery cathode investigated in this paper corresponds to 29% of the mass of Li-ion batteries and is made up of 83% LiCoO2, 14.5% C and less than 2.5% Al, Al2O3 and Co3O4. The use of spent Li-ion battery cathode tape increased the degradation velocity constant of methylene blue in the absence of light by about 200 times in relation to pure H2O2. This increase can be explained by a reduction in the activation energy from 83 kJ mol(-1) to 26 kJ mol(-1). The mechanism of degradation promoted by LiCoO2 is probably related to the generation of superoxide radical (O2(-)). The rupture of the aromatic rings of methylene blue was analyzed by ESI-MS. Copyright © 2015. Published by Elsevier Ltd.

  11. Reactivity of uranyl ion with quinquedentate chelating hydrazine derivatives. Pt. 2. 2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone)

    Energy Technology Data Exchange (ETDEWEB)

    Paolucci, G; Marangoni, G; Bandoli, G; Clemente, D A [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1980-01-01

    The new quinquedentate chelating ligand 2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone) (H/sub 2/dapmb) reacts with uranyl nitrate and perchlorate to give complexes which are described. All the complexes have been fully deprotonated to neutral species (UO/sub 2/(dapmb)), under a range of experimental conditions. This complex can be isolated in two different crystalline forms, ..cap alpha.. and ..beta.., depending on the experimental conditions. All the species have been characterized by a number of analytical and physico-chemical measurements, including the determination of the crystal structure of the two isomers of (UO/sub 2/(dapmb)). An accurate structure determination was carried out for the monoclinic modification, while the investigation of the orthorhombic form was undertaken merely to ascertain whether or not its configuration was the same as that of the monoclinic form. The geometry of (UO/sub 2/(dapmb)) in the two forms is very similar, the only significant difference being the conformation of a carbon atom in a methoxy-group. Seven-fold coordination of U/sup VI/ was found, with the five donor atoms in the equatorial plane and the linear UO/sub 2/ group normal to the plane. Interconversion reactions on the various compounds have been studied.

  12. Structure, Reactivity and Dynamics

    Indian Academy of Sciences (India)

    Understanding structure, reactivity and dynamics is the core issue in chemical ... functional theory (DFT) calculations, molecular dynamics (MD) simulations, light- ... between water and protein oxygen atoms, the superionic conductors which ...

  13. Supra-molecular structure and chemical reactivity of cellulose I studied using CP/MAS (sup)13 C-NMR

    CSIR Research Space (South Africa)

    Chunilall, Viren

    2013-08-01

    Full Text Available There are a few traditional methods of analysing the chemical properties of cellulose I. Some of these methods include the Permanganate number determination, which is used to obtain the lignin content of the pulp [12]. The acid insoluble lignin content... – Fundamental Aspects 88 [10] Fengel D, Wegener G. Wood Chemistry, Ultrastructure, Reactions, Walter de Gruyter; 1984. [11] Uhlmann T. Ullmann's encyclopedia of industrial chemistry. Paper and Pulp. 1991; 18 (A). [12] Permanganate number of pulp, Tappi T...

  14. Single and double carbon vacancies in pyrene as first models for graphene defects: A survey of the chemical reactivity toward hydrogen

    Science.gov (United States)

    Nieman, Reed; Das, Anita; Aquino, Adélia J. A.; Amorim, Rodrigo G.; Machado, Francisco B. C.; Lischka, Hans

    2017-01-01

    Graphene is regarded as one of the most promising materials for nanoelectronics applications. Defects play an important role in modulating its electronic properties and also enhance its chemical reactivity. In this work the reactivity of single vacancies (SV) and double vacancies (DV) in reaction with a hydrogen atom Hr is studied. Because of the complicated open shell electronic structures of these defects due to dangling bonds, multireference configuration interaction (MRCI) methods are being used in combination with a previously developed defect model based on pyrene. Comparison of the stability of products derived from Csbnd Hr bond formation with different carbon atoms of the different polyaromatic hydrocarbons is made. In the single vacancy case the most stable structure is the one where the incoming hydrogen is bound to the carbon atom carrying the dangling bond. However, stable Csbnd Hr bonded structures are also observed in the five-membered ring of the single vacancy. In the double vacancy, most stable bonding of the reactant Hr atom is found in the five-membered rings. In total, Csbnd Hr bonds, corresponding to local energy minimum structures, are formed with all carbon atoms in the different defect systems and the pyrene itself. Reaction profiles for the four lowest electronic states show in the case of a single vacancy a complex picture of curve crossings and avoided crossings which will give rise to a complex nonadiabatic reaction dynamics involving several electronic states.

  15. 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.

  16. Effective Remediation of Lead Ions from Aqueous Solution by Chemically Carbonized Rubber Wood Sawdust: Equilibrium, Kinetics, and Thermodynamic Study

    Directory of Open Access Journals (Sweden)

    Swarup Biswas

    2015-01-01

    Full Text Available Rubber wood sawdust was carbonized into charcoal by chemical treatment which was used for removal of lead ion from aqueous solution. The work involves batch experiments to investigate the pH effect, initial concentration of adsorbate, contact time, and adsorbent dose. Experimental data confirmed that the adsorption capacities increased with increasing inlet concentration and bed height and decreased with increasing flow rate. Adsorption results showed a maximum adsorption capacity of 37 mg/g at 308 K. Langmuir, Freundlich, and Temkin model adsorption isotherm models were applied to analyze the process where Temkin was found as a best fitted model for present study. Simultaneously kinetics of adsorption like pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were investigated. Thermodynamic parameters were used to analyze the adsorption experiment. Fourier transform infrared spectroscopy, scanning electron microscope, and energy dispersive X-ray spectroscopy confirmed the batch adsorption of lead ion onto chemically carbonized rubber wood sawdust.

  17. Radiation-chemical behaviour of neptunium ions in nitric acid solutions in the presence of curium-244

    International Nuclear Information System (INIS)

    Frolova, L.M.; Frolov, A.A.; Vasil'ev, V.Ya.

    1984-01-01

    Radiation-chemical behaviour of neptunium ions in nitric acid solutions is studied under the action of intensive internal alpha-irradiation conditioned by curium nuclides. In 0.3-1.1 mol/l solutions of nitric acid radiation-chemical oxidation of neptunium (4) and reduction of neptunium (6) is obeyed to the first order law of reaction rate in respect to neptunium concentration. Effective constants of neptunium (4) oxidation rates and neptuniumi(6) reduction rates are not dependent on neptunium ion in1tial concentration and increase with a growth of a dose rate of alpha-irradiation of solution. In equilibrium only neptunium (5) and neptunium (6) are present in solutions with HNO 3 concentration less than 1 mol/l. In more concentrated solutions equilibrium between sexa-, penta- and tetravalent neptunium forms is established. Equilibrium concentrations of neptunium valent forms are not dependent on neptunium initial oxidation state under the same initial conditions (dose rate, neptunium concentration and acidity. It is shown form experimental data that under the action of alpha-irradiation neptunium (5) both is oxidated to neptunium (6) and is reduced to neptunium (4)

  18. Fragmentation of molecular ions in differential mobility spectrometry as a method for identification of chemical warfare agents.

    Science.gov (United States)

    Maziejuk, M; Puton, J; Szyposzyńska, M; Witkiewicz, Z

    2015-11-01

    The subject of the work is the use of differential mobility spectrometry (DMS) for the detection of chemical warfare agents (CWA). Studies were performed for mustard gas, i.e., bis(2-chloroethyl)sulfide (HD), sarin, i.e., O-isopropyl methylphosphonofluoridate (GB) and methyl salicylate (MS) used as test compounds. Measurements were conducted with two ceramic DMS analyzers of different constructions allowing the generation of an electric field with an intensity of more than 120 Td. Detector signals were measured for positive and negative modes of operation in a temperature range from 0 to 80 °C. Fragmentations of ions containing analyte molecules were observed for all tested compounds. The effective temperatures of fragmentation estimated on the basis of dispersion plots were equal from about 148 °C for GB to 178 °C for MS. It was found that values of separation voltage (SV) and compensation voltage (CV) at which the fragmentation of sample ions is observed may be the parameters improving the certainty of detection for different analytes. The DMS analyzers enabling the observation of ion fragmentation can be successfully used for effective CWA detection. Copyright © 2015. Published by Elsevier B.V.

  19. Comparison of adsorption of Cd(II and Pb(II ions on pure and chemically modified fly ashes