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Sample records for hydrogenation disproportionation desorption

  1. Effect of hydrogenation disproportionation conditions on magnetic anisotropy in Nd-Fe-B powder prepared by dynamic hydrogenation disproportionation desorption recombination

    Masao Yamazaki

    2017-05-01

    Full Text Available Various anisotropic Nd-Fe-B magnetic powders were prepared by the dynamic hydrogenation disproportionation desorption recombination (d-HDDR treatment with different hydrogenation disproportionation (HD times (tHD. The resulting magnetic properties and microstructural changes were investigated. The magnetic anisotropy was decreased with increasing tHD. In the d-HDDR powders with higher magnetic anisotropy, fine (200–600 nm and coarse (600–1200 nm Nd2Fe14B grains were observed. The coarse Nd2Fe14B grains showed highly crystallographic alignment of the c-axis than fine Nd2Fe14B grains. In the highly anisotropic Nd2Fe14B d-HDDR powder, a large area fraction of lamellar-like structures consisting of NdH2 and α-Fe were observed after HD treatment. Furthermore, the mean diameter of the lamellar-like regions, where lamellar-like structures orientate to the same direction in the HD-treated alloys was close to that of coarse Nd2Fe14B grains after d-HDDR treatment. Thus, the lamellar-like regions were converted into the crystallographically aligned coarse Nd2Fe14B grains during desorption recombination treatment, and magnetic anisotropy is closely related to the volume fraction of lamellar-like regions observed after HD treatment.

  2. Preparation of Sm2Fe17-xGaxNy/Cy magnets by a hydrogenation-disproportionation-desorption-recombination process

    Kubis, M.; Cao, L.; Handstein, A.; Gebel, B.; Mueller, K.; Schultz, L.

    1997-01-01

    A hydrogenation-disproportionation-desorption-recombination process (HDDR) was applied to Sm 2 Fe 17-x Ga x (x=0.5, 1, and 2). The process was studied by means of temperature-pressure analysis, x-ray diffraction and scanning electron microscopy. It was shown that Ga not only stabilizes the interstitially modified compounds Sm 2 Fe 17-x Ga x C y (0 2 Fe 17-x Ga x against the disproportionation by hydrogen. Therefore, only for x=0.5 can a nearly complete HDDR be performed. The HDDR-treated and subsequently nitrogenated or carburized samples show coercivities μ 0J H C up to 3.1 T and 2.5 T, respectively. Hot compaction increases the density of the Sm 2 Fe 16.5 Ga 0.5 C y powder; however, it leads to a loss of coercivity due to decomposition into α-iron and samarium carbides. copyright 1997 American Institute of Physics

  3. Hydrogenation-disproportionation-desorption-recombination in Sm2Fe16M (M=Al, Ga and Si) and magnetic properties of their carburized powders

    Kubis, M.; Rave, W.; Cao, L.; Gebel, B.; Mueller, K.-H.; Schultz, L.

    1998-01-01

    The application of the hydrogenation-disproportionation-desorption-recombination (HDDR) process in Sm 2 Fe 16 M (M=Al,Ga and Si) was investigated. The hydrogen absorption behaviour was studied by temperature-pressure analysis (TPA). In the temperature range between 500 and 800 C, Sm 2 Fe 16 M samples with M=Ga and Si show a weaker hydrogen absorption than Sm 2 Fe 16 Al. This was confirmed by X-ray diffraction which showed a complete disproportionation of Sm 2 Fe 16 Al into SmH z (1.9 2 Fe 16 Ga and Sm 2 Fe 16 Si exhibit a fraction of undecomposed material with the Th 2 Zn 17 -type structure after the disproportionation procedure. These results point to a stabilization of Sm 2 Fe 16 M against disproportionation by hydrogen for M=Ga and Si. The magnetization processes of carburized HDDR powders were studied by VSM measurements and Kerr microscopy. The demagnetization curve of our HDDR processed Sm 2 Fe 16 AlC y is well shaped, whereas those of Sm 2 Fe 16 GaC y and Sm 2 Fe 16 SiC y show a large decrease of the polarization at low fields. The favourable behaviour of Sm 2 Fe 16 AlC y is due to a homogeneous submicron grain structure. In Sm 2 Fe 16 GaC y and Sm 2 Fe 16 SiC y samples, an additional, magnetically soft phase with larger domains was observed which causes the low coercivity. As a consequence, HDDR was only favourable for the preparation of Sm 2 Fe 16 MC y hard magnets with M=Al but not for M=Ga and Si. Optimization of the HDDR process in Sm 2 Fe 16 Al and subsequent nitrogenation or carburization led to coercivities of μ 0j H c =2.9 and 2.5 T, respectively. (orig.)

  4. Hydrogenation-disproportionation-desorption-recombination in Sm{sub 2}Fe{sub 16}M (M=Al, Ga and Si) and magnetic properties of their carburized powders

    Kubis, M.; Rave, W.; Cao, L.; Gebel, B.; Mueller, K.-H.; Schultz, L. [Institut fuer Festkoerper- und Werkstofforschung Dresden e.V. (Germany)

    1998-11-20

    The application of the hydrogenation-disproportionation-desorption-recombination (HDDR) process in Sm{sub 2}Fe{sub 16}M (M=Al,Ga and Si) was investigated. The hydrogen absorption behaviour was studied by temperature-pressure analysis (TPA). In the temperature range between 500 and 800 C, Sm{sub 2}Fe{sub 16}M samples with M=Ga and Si show a weaker hydrogen absorption than Sm{sub 2}Fe{sub 16}Al. This was confirmed by X-ray diffraction which showed a complete disproportionation of Sm{sub 2}Fe{sub 16}Al into SmH{sub z} (1.9disproportionation procedure. These results point to a stabilization of Sm{sub 2}Fe{sub 16}M against disproportionation by hydrogen for M=Ga and Si. The magnetization processes of carburized HDDR powders were studied by VSM measurements and Kerr microscopy. The demagnetization curve of our HDDR processed Sm{sub 2}Fe{sub 16}AlC{sub y} is well shaped, whereas those of Sm{sub 2}Fe{sub 16}GaC{sub y} and Sm{sub 2}Fe{sub 16}SiC{sub y} show a large decrease of the polarization at low fields. The favourable behaviour of Sm{sub 2}Fe{sub 16}AlC{sub y} is due to a homogeneous submicron grain structure. In Sm{sub 2}Fe{sub 16}GaC{sub y} and Sm{sub 2}Fe{sub 16}SiC{sub y} samples, an additional, magnetically soft phase with larger domains was observed which causes the low coercivity. As a consequence, HDDR was only favourable for the preparation of Sm{sub 2}Fe{sub 16}MC{sub y} hard magnets with M=Al but not for M=Ga and Si. Optimization of the HDDR process in Sm{sub 2}Fe{sub 16}Al and subsequent nitrogenation or carburization led to coercivities of {mu}{sub 0j}H{sub c}=2.9 and 2.5 T, respectively. (orig.) 11 refs.

  5. Nanocrystalline NdFeB magnet prepared by mechanically activated disproportionation and desorption-recombination in-situ sintering

    Xiaoya, Liu; Yuping, Li; Lianxi, Hu

    2013-01-01

    The process of mechanically activated disproportionation and desorption-recombination in-situ sintering was proposed to synthesize highly densified nanocrystalline NdFeB magnet, and its validity was demonstrated by experimental investigation with the use of a Nd 16 Fe 76 B 8 (atomic ratio) alloy. Firstly, the as-cast alloy was disproportionated by mechanical milling in hydrogen, with the starting micron-sized Nd 2 Fe 14 B phase decomposed into an intimate mixture of nano-structured NdH 2.7 , Fe 2 B and α-Fe phases. The as-disproportionated alloy powders were compacted by cold pressing and then subjected to desorption-recombination in-situ sintering. The microstructure of both the as-disproportionated and the subsequently sintered samples was characterized by X-ray diffraction and electron transmission microscopy, respectively. The magnetic properties of the sintered samples were measured by using vibrating sample magnetometer. The results showed that, by vacuum sintering, not only was the powder compact consolidated, but also the as-disproportionated microstucture transformed into nanocrystalline Nd 2 Fe 14 B phase via the well-known desorption-recombination reaction, thus giving rise to nanocrystalline NdFeB magnet. In the present study, the optimal sintering parameters were found to be 780 °C×30 min. In this case, the coercivity, the remanence, and maximum energy product of the magnet sample achieved 0.8 T, 635.3 kA/m, and 106.3 kJ/m 3 , respectively. - Highlights: ► Nano-structured disproportionated NdFeB alloy powders by mechanical milling in hydrogen. ► Highly densified green magnet compact by cold pressing of as-disproportionated NdFeB alloy powders. ► Nanocrystalline NdFeB magnets by desorption-recombination in-situ sintering under vacuum. ► Magnetic properties significantly improved by relative density enhancement and nanocrystallization of Nd 2 Fe 14 B phase. ► The effects of sintering parameters on magnetic properties and the underlying

  6. Nanocrystalline NdFeB magnet prepared by mechanically activated disproportionation and desorption-recombination in-situ sintering

    Xiaoya, Liu; Yuping, Li [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Lianxi, Hu, E-mail: hulx@hit.edu.cn [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China)

    2013-03-15

    The process of mechanically activated disproportionation and desorption-recombination in-situ sintering was proposed to synthesize highly densified nanocrystalline NdFeB magnet, and its validity was demonstrated by experimental investigation with the use of a Nd{sub 16}Fe{sub 76}B{sub 8} (atomic ratio) alloy. Firstly, the as-cast alloy was disproportionated by mechanical milling in hydrogen, with the starting micron-sized Nd{sub 2}Fe{sub 14}B phase decomposed into an intimate mixture of nano-structured NdH{sub 2.7}, Fe{sub 2}B and {alpha}-Fe phases. The as-disproportionated alloy powders were compacted by cold pressing and then subjected to desorption-recombination in-situ sintering. The microstructure of both the as-disproportionated and the subsequently sintered samples was characterized by X-ray diffraction and electron transmission microscopy, respectively. The magnetic properties of the sintered samples were measured by using vibrating sample magnetometer. The results showed that, by vacuum sintering, not only was the powder compact consolidated, but also the as-disproportionated microstucture transformed into nanocrystalline Nd{sub 2}Fe{sub 14}B phase via the well-known desorption-recombination reaction, thus giving rise to nanocrystalline NdFeB magnet. In the present study, the optimal sintering parameters were found to be 780 Degree-Sign C Multiplication-Sign 30 min. In this case, the coercivity, the remanence, and maximum energy product of the magnet sample achieved 0.8 T, 635.3 kA/m, and 106.3 kJ/m{sup 3}, respectively. - Highlights: Black-Right-Pointing-Pointer Nano-structured disproportionated NdFeB alloy powders by mechanical milling in hydrogen. Black-Right-Pointing-Pointer Highly densified green magnet compact by cold pressing of as-disproportionated NdFeB alloy powders. Black-Right-Pointing-Pointer Nanocrystalline NdFeB magnets by desorption-recombination in-situ sintering under vacuum. Black-Right-Pointing-Pointer Magnetic properties significantly

  7. Modeling of hydrogen desorption from tungsten surface

    Guterl, J., E-mail: jguterl@ucsd.edu [University of California, San Diego, La Jolla, CA 92093 (United States); Smirnov, R.D. [University of California, San Diego, La Jolla, CA 92093 (United States); Krasheninnikov, S.I. [University of California, San Diego, La Jolla, CA 92093 (United States); Nuclear Research National University MEPhI, Moscow 115409 (Russian Federation); Uberuaga, B.; Voter, A.F.; Perez, D. [Los Alamos National Laboratory, Los Alamos, NM 8754 (United States)

    2015-08-15

    Hydrogen retention in metallic plasma-facing components is among key-issues for future fusion devices. For tungsten, which has been chosen as divertor material in ITER, hydrogen desorption parameters experimentally measured for fusion-related conditions show large discrepancies. In this paper, we therefore investigate hydrogen recombination and desorption on tungsten surfaces using molecular dynamics simulations and accelerated molecular dynamics simulations to analyze adsorption states, diffusion, hydrogen recombination into molecules, and clustering of hydrogen on tungsten surfaces. The quality of tungsten hydrogen interatomic potential is discussed in the light of MD simulations results, showing that three body interactions in current interatomic potential do not allow to reproduce hydrogen molecular recombination and desorption. Effects of surface hydrogen clustering on hydrogen desorption are analyzed by introducing a kinetic model describing the competition between surface diffusion, clustering and recombination. Different desorption regimes are identified and reproduce some aspects of desorption regimes experimentally observed.

  8. Intermediate phases in the hydrogen disproportionated state of NdFeB-type powders

    Yi, G.; Chapman, J. N.; Brown, D. N.; Harris, I. R.

    2001-01-01

    Transmission electron microscopy studies have been carried out on partially disproportionated NdFeB-type alloys. A new intermediate magnetic (NIM) phase has been identified. Moreover, the lamella structure which subsequently develops from the tetragonal NIM phase comprises a tetragonal NdFe-containing (IL) phase and α-Fe. The experimental data show strong evidence of a well-defined crystallographic relation between both the NIM and lamella phases and between the IL phase and α-Fe. These observations give insight into how crystallographic texture, and hence anisotropy, can be developed in NdFeB-type powders processed by the hydrogenation, disproportionation, desorption, and recombination route. copyright 2001 American Institute of Physics

  9. Study on hydrogen absorption/desorption properties of uranium alloys

    Ito, Hiroshi; Yamaguchi, Kenji; Yamawaki, Michio [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab.

    1996-10-01

    Hydrogen absorption/desorption properties of two U-Mn intermetallic compounds, U{sub 6}Mn and UMn{sub 2}, were investigated. U{sub 6}Mn absorbed hydrogen and the hydrogen desorption pressure of U{sub 6}Mn obtained from this experiment was higher than that of U, which was considered to be the effect of alloying, whereas UMn{sub 2} was not observed to absorb hydrogen up to 50 atm at room temperature. (author)

  10. Acoustic emission during hydrogen absorption and desorption in palladium

    Ramesh, R.; Mukhopadhyay, C.K.; Jayakumar, T.; Baldev Raj

    1996-01-01

    Acoustic emission technique has been used to study charging and discharging of hydrogen in palladium. During charging, breaking of oxide film due to surface activation and saturation of hydrogen absorption have been identified by acoustic emission. In the discharging cycle, the desorption of hydrogen from the specimen leads to high AE activity immediately after initiation of discharging, followed by gradual decrease in the acoustic activity, which reaches a minimum upon completion of the desorption. The potential of the acoustic emission technique for studying the kinetics of hydrogen absorption and desorption in metals has been shown. (author)

  11. Kinetics of Hydrogen Absorption and Desorption in Titanium

    Suwarno Suwarno

    2017-10-01

    Full Text Available Titanium is reactive toward hydrogen forming metal hydride which has a potential application in      energy storage and conversion. Titanium hydride has been widely studied for hydrogen storage, thermal storage, and battery electrodes applications. A special interest is using titanium for hydrogen production in a hydrogen sorption-enhanced steam reforming of natural gas. In the present work, non-isothermal dehydrogenation kinetics of titanium hydride and kinetics of hydrogenation in gaseous flow at isothermal conditions were investigated. The hydrogen desorption was studied using temperature desorption spectroscopy (TDS while the hydrogen absorption and desorption in gaseous flow were studied by temperature programmed desorption (TPD. The present work showed that the path of dehydrogenation of the TiH2 is d®b®a hydride phase with possible overlapping steps occurred. The fast hydrogen desorption rate observed at the TDS main peak temperature were correlated with the fast transformation of the d-TiH1.41 to b-TiH0.59. In the gaseous flow, hydrogen absorption and desorption were related to the transformation of b-TiH0.59 Û d-TiH1.41 with 2 wt.% hydrogen reversible content. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 20th March 2017; Accepted: 9th April 2017; Available online: 27th October 2017; Published regularly: December 2017 How to Cite: Suwarno, S., Yartys, V.A. (2017. Kinetics of Hydrogen Absorption and Desorption in Titanium. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3: 312-317  (doi:10.9767/bcrec.12.3.810.312-317

  12. Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

    King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F. [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Nemanich, Robert J. [Department of Physics, North Carolina State University, Raleigh, North Carolina 27695 (United States)

    2015-09-15

    Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and

  13. Modelling of discrete TDS-spectrum of hydrogen desorption

    Rodchenkova, Natalia I.; Zaika, Yury V.

    2015-12-01

    High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

  14. Modelling of discrete TDS-spectrum of hydrogen desorption

    Rodchenkova, Natalia I; Zaika, Yury V

    2015-01-01

    High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition. (paper)

  15. Hydrogen absorption-desorption properties of U2Ti

    Yamamoto, Takuya; Tanaka, Satoru; Yamawaki, Michio

    1990-01-01

    Hydrogen absorption-desorption properties of U 2 Ti intermetallic compound was examined over the temperature range of 298 to 973 K and at hydrogen pressures below 10 5 Pa. It absorbs hydrogen up to 7.6 atoms per F.U. (formula unit) by two step reactions and hence each desorption isotherm is separated into two plateau regions. In the first plateau, a newly-found ternary hydride is formed, where the hydrogen concentration, c H , reaches 2.4 H atoms/F.U. In the second plateau, UH 3 is formed and c H reaches 7.6 H atoms/F.U. The specimen is disintegrated into fine powder in the second plateau, while in the first plateau the ternary hydride which was identified to be UTi 2 H x (x=4.8 to 6.2) showed high durability against powdering. It is predicted that UTi 2 can be suitable material for tritium storage. (orig.)

  16. Hydrogen induced dis-proportionation studies on Zr-Co-M (M=Ni, Fe, Ti) ternary alloys

    Jat, Ram Avtar; Pati, Subhasis; Parida, S.C.; Agarwal, Renu; Mukerjee, S.K.; Sastry, P.U.; Jayakrishnan, V.B.

    2016-01-01

    The intermetallic compound ZrCo is considered as a suitable material for storage, supply and recovery of hydrogen isotopes in International Thermonuclear Experimental Reactor (ITER). However, upon repeated hydriding-dehydriding cycles, the hydrogen storage capacity of ZrCo decreases, which is attributed to the disproportionate reaction ZrCo + H 2 ↔ ZrH 2 + ZrCo 2 . The reduction of hydrogen storage capacity of ZrCo is not desirable for its use in tritium facilities. In our previous studies, attempts were made to improve the durability of ZrCo against dis-proportionation by including a third element. The present study is aimed to investigate the hydrogen induced dis-proportionation of Zr-Co-M (M=Ni, Fe and Ti) ternary alloys under hydrogen delivery conditions

  17. Hydrogen absorption-desorption at metal surfaces

    Ward, C.A.; Pataki, L.

    1991-04-01

    On the basis of experimental studies, it has been proposed that when zirconium oxide (ZrO 2 ) is exposed to hydrogen at 300 degrees C or higher, a reaction occurs to produce metallic zirconium and water, thereby increasing the electrical conductivity of the oxide film and its permeability to hydrogen. A series of experiments has been performed in which specimens of zirconium and zirconium-2.5% niobium were either hydrided or deuterided in a furnace at a temperature between 300 degrees C and 800 degrees C and in an atmosphere that consisted primarily of either hydrogen (H 2 ) or deuterium (D 2 ). After cooling a specimen to room temperature, it was placed in a thermogravimetric analyzer that was equipped with a mass spectrometer, TGA-MS. Each specimen was then heated to 1200 degrees C at a controlled rate in a primarily helium atmosphere monitored with the mass spectrometer. Light water (H 2 O) evolved from the hydrided specimens and heavy water (D 2 0) from the deuterided ones and there was a weight loss of the specimens that accompanied the water evolution. The specimens having approximately the same amount of hydride but more oxide also evolved more H 2 O, and that the H 2 O did not come from reactions between impurity H 2 and oxygen (O 2 ) in the TGA-MS. Heating a zirconium or zirconium alloy specimen that contains a hydride or deuteride phase within and an oxide layer on its surface causes the hydrogen to diffuse toward the surface and when it encounters the oxide a reaction follows that produces water. The conventional mechanism for the dissipation of the imperviousness of ZrO 2 to H 2 that results from the oxide being exposed to a reducing atmosphere will not explain the water production observed in these experiments. However, the existence of the proposed reaction can account for the elevated hydrogen concentration in an oxide film that has been observed to accompany the aqueous corrosion of zirconium and the effects on both the electrical conductivity and

  18. Thermal desorption spectroscopy for investigating hydrogen isotope behavior in materials

    Xia Tirui; Yang Hongguang; Zhan Qin; Han Zhibo; He Changshui

    2012-01-01

    The behavior of hydrogen isotope generated in fusion reactor materials is the key issue for safety and economic operation of fusion reactors and becomes an interesting field. In order to investigate the mechanism of hydrogen isotope such as diffusion, release and retention, a high-sensitivity thermal desorption spectroscopy (TDS) in combination with a quadruple mass spectrometer (QMS) was developed. A major technical breakthrough in ultrahigh vacuum (UHV), low hydrogen background, linear heating and sensitivity calibration of TDS system was made. UHV of l × 10 -7 Pa and low hydrogen background of l × 10 -9 Pa were obtained by combining turbo molecule pump and sputter ion pump. Specimens can be linearly heated up to 1173 K at the rate of 1 to 50 K/min under the MCGS PID software. Sensitivity calibration of the TDS system was accomplished using a special deuterium leak in the detector mode of QMS second electron multiplier. The desorption sensitivity coefficient and the minimum detection limit of deuterium desorption rate are 6.22 × l0 24 s -l · and l.24 × l0 -10 s -1 , respectively. The measurement was also routinely conducted on a specimen of standard, deuterium-containing Zr-4 alloy maintained in the laboratory, so as to validate the TDS method. (authors)

  19. Hydrogen Temperature-Programmed Desorption in Platinum Catalysts: Decomposition and Isotopic Exchange by Spillover Hydrogen of Chemisorbed Ammonia.

    Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Barr, M.K.; Modica, F.S.

    1996-01-01

    H{2}-TPD of Pt/alumina catalysts display multiple hydrogendesorptions. In addition to chemisorbed hydrogen (Peak I) atapproximately 175}o{C, there is a small hydrogen desorption (PeakII) at about 250}o{C and a large, irreversible hydrogen desorption(Peak III) at 450}o{C. The quantity of hydrogen

  20. Hydrogen Temperature-Programmed Desorption (H2 TPD) of Supported Platinum Catalysts.

    Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Modica, F.S.; Lane, G.S.; Vaarkamp, M.

    1993-01-01

    Hydrogen temperature-programmed desorption (TPD) of supported platinum catalysts, Pt/KLTL, Pt/H-LTL, Pt/K-MAZ, Pt/H-MAZ, Pt/-Al2O3, and Pt/SiO2, was performed after hydrogen reduction at 300, 450, or 650°C. For all catalysts, reversible desorption of chemisorbed hydrogen occurred at approximately

  1. Laser induced desorption as hydrogen retention diagnostic method

    Zlobinski, Miroslaw

    2016-07-15

    Laser Induced Desorption Spectroscopy (LIDS) is a diagnostic method to measure the hydrogen content in the surface of a material exposed to a hydrogen isotope (H,D,T) plasma. It is developed mainly to monitor hydrogen retention in the walls of magnetic fusion devices that have to limit the amount of their fuel tritium mainly due to safety reasons. The development of fusion increasingly focusses on plasma-wall interactions for which in situ diagnostics like LIDS are required that work during plasma operation and without tile removal. The method has first been developed for thin amorphous hydrocarbon (a-C:H < 500 nm) layers successfully and is studied in the present work on thick (15 μm) layers, carbon fibre composites (CFCs), bulk tungsten (W), W fuzz and mixed C/W materials. In LID a 3 ms Nd:YAG (1064 nm) laser pulse heats a spot of diameter 3 mm with 500 {sup MW}/{sub m{sup 2}} on W to 1800 K at the surface and thus above 1300 K within ca. 0.2 mm depth. On C materials (graphite, CFC, a-C:H) this temperature guarantees a nearly complete (>95%) desorption already within 1.5 ms pulse duration. The retained hydrogen atoms are desorbed locally, recombine to molecules and migrate promptly to the surface via internal channels like pores and grain boundaries. Whereas, in W the retained hydrogen atoms have to diffuse through the bulk material, which is a relatively slow process also directed into the depth. The desorbed hydrogen fraction can thus be strongly reduced to 18-91% as observed here. This fraction is measured by melting the central part of a previously heated spot ca. 40 μm deep with a diameter 2 mm, 3 ms laser pulse, releasing the remaining hydrogen. W samples exposed to different plasmas in TEXTOR, Pilot-PSI, PSI-2, PADOS and PlaQ show that the desorption fraction of LID mainly decreases due to higher sample temperature during plasma exposure. The heat causes deeper hydrogen diffusion and/or stronger hydrogen trapping due to creation of traps with higher

  2. Laser induced desorption as hydrogen retention diagnostic method

    Zlobinski, Miroslaw

    2016-01-01

    Laser Induced Desorption Spectroscopy (LIDS) is a diagnostic method to measure the hydrogen content in the surface of a material exposed to a hydrogen isotope (H,D,T) plasma. It is developed mainly to monitor hydrogen retention in the walls of magnetic fusion devices that have to limit the amount of their fuel tritium mainly due to safety reasons. The development of fusion increasingly focusses on plasma-wall interactions for which in situ diagnostics like LIDS are required that work during plasma operation and without tile removal. The method has first been developed for thin amorphous hydrocarbon (a-C:H < 500 nm) layers successfully and is studied in the present work on thick (15 μm) layers, carbon fibre composites (CFCs), bulk tungsten (W), W fuzz and mixed C/W materials. In LID a 3 ms Nd:YAG (1064 nm) laser pulse heats a spot of diameter 3 mm with 500 MW / m 2 on W to 1800 K at the surface and thus above 1300 K within ca. 0.2 mm depth. On C materials (graphite, CFC, a-C:H) this temperature guarantees a nearly complete (>95%) desorption already within 1.5 ms pulse duration. The retained hydrogen atoms are desorbed locally, recombine to molecules and migrate promptly to the surface via internal channels like pores and grain boundaries. Whereas, in W the retained hydrogen atoms have to diffuse through the bulk material, which is a relatively slow process also directed into the depth. The desorbed hydrogen fraction can thus be strongly reduced to 18-91% as observed here. This fraction is measured by melting the central part of a previously heated spot ca. 40 μm deep with a diameter 2 mm, 3 ms laser pulse, releasing the remaining hydrogen. W samples exposed to different plasmas in TEXTOR, Pilot-PSI, PSI-2, PADOS and PlaQ show that the desorption fraction of LID mainly decreases due to higher sample temperature during plasma exposure. The heat causes deeper hydrogen diffusion and/or stronger hydrogen trapping due to creation of traps with higher binding energy

  3. The Absorption-Desorption of Hydrogen by 1.5 g Depleted Uranium

    Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Si-Hyung; Kim, Kwang-Rag; Ahn, Do-Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Sohn, Soon Hwan; Song, Kyu Min [Korea Electric Power Research Institute, Daejeon (Korea, Republic of)

    2008-10-15

    The form of metal tritides is one of the most popular methods for the storage of hydrogen isotopes. Particularly when metal is in a powder form, the storage capacity of hydrogen isotopes become the maximum value. Here, a 1.5g depleted uranium metal was decrepitated into a powder upon an absorption and desorption of hydrogen gas. The conditions for an activation, absorption-desorption of the hydrogen were defined.

  4. The Absorption-Desorption of Hydrogen by 1.5 g Depleted Uranium

    Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Si-Hyung; Kim, Kwang-Rag; Ahn, Do-Hee; Sohn, Soon Hwan; Song, Kyu Min

    2008-01-01

    The form of metal tritides is one of the most popular methods for the storage of hydrogen isotopes. Particularly when metal is in a powder form, the storage capacity of hydrogen isotopes become the maximum value. Here, a 1.5g depleted uranium metal was decrepitated into a powder upon an absorption and desorption of hydrogen gas. The conditions for an activation, absorption-desorption of the hydrogen were defined

  5. Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

    Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

    2016-05-30

    Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

  6. Hydrogen desorption reactions of Li-N-H hydrogen storage system: Estimation of activation free energy

    Matsumoto, Mitsuru; Haga, Tetsuya; Kawai, Yasuaki; Kojima, Yoshitsugu

    2007-01-01

    The dehydrogenation reactions of the mixtures of lithium amide (LiNH 2 ) and lithium hydride (LiH) were studied under an Ar atmosphere by means of temperature programmed desorption (TPD) technique. The dehydrogenation reaction of the LiNH 2 /LiH mixture was accelerated by addition of 1 mol% Ti(III) species (k = 3.1 x 10 -4 s -1 at 493 K), and prolonged ball-milling time (16 h) further enhanced reaction rate (k = 1.1 x 10 -3 s -1 at 493 K). For the hydrogen desorption reaction of Ti(III) doped samples, the activation energies estimated by Kissinger plot (95 kJ mol -1 ) and Arrhenius plot (110 kJ mol -1 ) were in reasonable agreement. The LiNH 2 /LiH mixture without Ti(III) species, exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of the LiNH 2 /LiH mixture

  7. Hydrogen desorption from mechanically milled carbon micro coils hydrogenated at high temperature

    Yoshio Furuya; Shuichi Izumi; Seiji Motojima; Yukio Hishikawa

    2005-01-01

    Carbon micro coils (CMC) have been prepared by the catalytic pyrolysis of acetylene at 750-800 C. The as grown coils have an almost amorphous structure and contain about 1 mass% hydrogen. They have 0.1 - 10 mm coil length, 1-5 μm coil diameter, 0.1-0.5 μm coil pitch and about 100 m 2 /g specific surface area. They were graphitized, as maintaining the morphology of the coils, by heat-treating at a higher temperature than 2500 C in Ar atmosphere. The layer space (d) of graphitized CMC was determined to be 0.341 nm, forming a 'herringbone' structure with an inclination of 10-40 degree versus the coiled fiber axis, having a specific surface area of about 8 m 2 /g. The hydrogen absorption behaviors of CMC were investigated from RT to 1200 C by a thermal desorption spectrometry (TDS) using a quadrupole mass analyzer. In TDS measurements, pre-existing hydrogen, which was due to the residual acetylene incorporated into CMC on its growing, desorbed from 700 C and peaked at about 900 C. The increment in the main peak of desorbed hydrogen in the as-grown CMC heat-treated at 500 C for 1 h under high pressure of hydrogen gas (1.9 or 8.9 MPa) was not remarkable as is shown in Fig.1. While, in the CMC samples milled mechanically for 1 h at RT using a planetary ball mill, the increase of desorbed hydrogen became to be great with the hydrogen pressure (up to 8.9 MPa) on heat-treating at 500 C, as is shown in Fig.2. In these CMC samples, the building up temperature of the hydrogen desorption was shifted to a lower one and the temperature range of desorption became to be wider than those in the as-grown CMC because of the appearance of another desorption peak at about 600 C in addition to the peak ranging from 850 C to 900 C. The same kind of peak was also slightly observed in as-grown CMC (Fig.1). It is clear that this desorption at about 600 C has contributed to the remarkable increase of desorbed hydrogen in the milled CMC. In this work, values of more than 2 mass% were obtained

  8. STM-Induced Hydrogen Desorption via a Hole Resonance

    Stokbro, Kurt; Thirstrup, C.; Sakurai, M.

    1998-01-01

    We report STM-induced desorption of H from Si(100)-H(2 X 1) at negative sample bias. The desorption rate exhibits a power-law dependence on current and a maximum desorption rate at -7 V. The desorption is explained by vibrational heating of H due to inelastic scattering of tunneling holes...... with the Si-H 5 sigma hole resonance. The dependence of desorption rate on current and bias is analyzed using a novel approach for calculating inelastic scattering, which includes the effect of the electric field between tip and sample. We show that the maximum desorption rate at -7 V is due to a maximum...

  9. Investigation of hydrogen-deformation interactions in β-21S titanium alloy using thermal desorption spectroscopy

    Tal-Gutelmacher, E.; Eliezer, D.; Boellinghaus, Th.

    2007-01-01

    The focus of this paper is the investigation of the combined influence of hydrogen and pre-plastic deformation on hydrogen's absorption/desorption behavior, the microstructure and microhardness of a single-phased β-21S alloy. In this study, thermal desorption analyses (TDS) evaluation of various desorption and trapping parameters provide further insight on the relationships between hydrogen absorption/desorption processes and deformation, and their mutual influence on the microstructure and the microhardness of β-21S alloy. TDS spectra were supported by other experimental techniques, such as X-ray diffraction, scanning and transmission electron microscopy, hydrogen quantity analyses and microhardness tests. Pre-plastic deformation, performed before the electrochemical hydrogenation of the alloy, increased significantly the hydrogen absorption capacity. Its influence was also evident on the notably expanded lattice parameter of β-21S alloy after hydrogenation. However, no hydride precipitation was observed. An interesting softening effect of the pre-deformed hydrogenated alloy was revealed by microhardness tests. TDS demonstrated the significant effect of pre-plastic deformation on the hydrogen evolution process. Hydrogen desorption temperature and the activation energy for hydrogen release increased, additional trap states were observed and the amount of desorbed hydrogen decreased

  10. Effect of long-term hydrogen absorption/desorption cycling on hydrogen storage properties of MmNi3.55Co0.75Mn0.4Al0.3

    Li, S.L.; Chen, W.; Chen, D.M.; Yang, K.

    2009-01-01

    The effect of a long-term hydrogen absorption/desorption cycling up to 2000 cycles on the hydrogen storage properties of MmNi 3.55 Co 0.75 Mn 0.4 Al 0.3 alloy was investigated. The pressure-composition (PC) isotherms for absorption/desorption and absorption kinetics were measured at 338 K, 353 K and 368 K both after initial activation and 2000 cycles. X-ray diffraction analysis revealed that the alloy had a homogeneous hexagonal CaCu 5 type structure and kept this structure even after 2000 hydrogen absorption/desorption cycles. It is found that the absorption/desorption plateau pressures were lowered, the storage capacity and the absorption kinetics were slightly degraded and the hysteresis loss was increased at all the investigated temperatures after 2000 cycles. It is also found that the particle size after 2000 cycles was much smaller compared to that after initial activation. The change of the hydrogen absorption/desorption properties of the alloy after 2000 cycles has been explained by considering the crystal structure, disproportionation property, pulverization of the sample and the impurities in the charging hydrogen employed in cycling

  11. Hydrogen desorption kinetics from zirconium hydride and zirconium metal in vacuum

    Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.

    2014-01-01

    The kinetics of hydrogen desorption from zirconium hydride is important in many nuclear design and safety applications. In this paper, a coordinated experimental and modeling study has been used to explicitly demonstrate the applicability of existing kinetic theories for hydrogen desorption from zirconium hydride and α-zirconium. A static synthesis method was used to produce δ-zirconium hydride, and the crystallographic phases of the zirconium hydride were confirmed by X-ray diffraction (XRD). Three obvious stages, involving δ-zirconium hydride, a two-phase region, and α-zirconium, were observed in the hydrogen desorption spectra of two zirconium hydride specimens with H/Zr ratios of 1.62 and 1.64, respectively, which were obtained using thermal desorption spectroscopy (TDS). A continuous, one-dimensional, two-phase moving boundary model, coupled with the zero- and second-order kinetics of hydrogen desorption from δ-zirconium hydride and α-zirconium, respectively, has been developed to reproduce the TDS experimental results. A comparison of the modeling predictions with the experimental results indicates that a zero-order kinetic model is valid for description of hydrogen flux away from the δ-hydride phase, and that a second-order kinetic model works well for hydrogen desorption from α-Zr if the activation energy of desorption is optimized to be 70% of the value reported in the literature

  12. Temperature suppression of STM-induced desorption of hydrogen on Si(100) surfaces

    Thirstrup, C.; Sakurai, M.; Nakayama, T.

    1999-01-01

    The temperature dependence of hydrogen (H) desorption from Si(100) H-terminated surfaces by a scanning tunneling microscope (STM) is reported for negative sample bias. It is found that the STM induced H desorption rate (R) decreases several orders of magnitude when the substrate temperature...

  13. Beneficial effect of carbon on hydrogen desorption kinetics from Mg–Ni–In alloy

    Cermak, J.; Kral, L.

    2013-01-01

    Highlights: ► Beneficial effect of graphitic carbon was observed. ► The effect is optimal up to c opt . ► Above c opt , phase decomposition occurs. ► Indium in studied Mg–Ni-based alloys prevents oxidation. - Abstract: In the present paper, hydrogen desorption kinetics from hydrided Mg–Ni–In–C alloys was investigated. A chemical composition that substantially accelerates hydrogen desorption was found. It was observed that carbon improves the hydrogen desorption kinetics significantly. Its beneficial effect was found to be optimum close to the carbon concentration of about c C ≅ 5 wt.%. With this composition, stored hydrogen can be desorbed readily at temperatures down to about 485 K, immediately after hydrogen charging. This can substantially shorten the hydrogen charging/discharging cycle of storage tanks using Mg–Ni-based alloys as hydrogen storage medium. For higher carbon concentrations, unwanted phases precipitated, likely resulting in deceleration of hydrogen desorption and lower hydrogen storage capacity.

  14. GaN CVD Reactions: Hydrogen and Ammonia Decomposition and the Desorption of Gallium

    Bartram, Michael E.; Creighton, J. Randall

    1999-01-01

    Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N 15 H 3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N 2 of mixed isotopes below the onset of GaN sublimation, This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence G-aN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia

  15. Property changes of some hydrogen storage alloys upon hydrogen absorption-desorption cycling

    Park, C.N.; Cho, S.W.; Choi, J.

    2005-01-01

    Hydrogen absorption-desorption cycling induced by pressure change in a closed system were carried out with LaNi 5 , La 0.7 Ce 0.3 Ni 4 Cu and TiFe 0.9 Ni 0.1 alloys. PC isotherms measured during the cycling showed some changes in hydrogen storage capacity, plateau pressure and hysteresis of the alloys. The half capacity life of LaNi 5 alloy can be projected as 70,000 cycles for room temperature pressure cycling. When La 0.7 Ce 0.3 Ni 4 Cu alloy was pressure cycled both of the plateau pressures were decreased significantly and continuously. TiFe 0.9 Ni 0.1 alloy showed a good resistance to cyclic degradation. Heat treatments of the degraded alloys under 1 atm of hydrogen gas recovered most of the hydrogen storage properties to the initial level even though they were degraded again more rapidly upon subsequent cycling. (orig.)

  16. Thermal desorption of hydrogen from Mg2Ni hydrogen storage materials.

    Hur, Tae Hong; Han, Jeong Seb; Kim, Jin Ho; Kim, Byung Kwan

    2011-07-01

    In order to investigate the influence of HCS on the hydrogen occupation site of Mg2Ni alloy, the thermal desorption technique has been applied to Mg2Ni hydride made by hydriding combustion synthesis (HCS). Mg2Ni was made under low temperature in a short time by the HCS compared to conventional melting process. At various initial hydride wt% from 0.91 to 3.52, the sample was heated to 623 K at a rate of 1.0 K/min. The starting temperature of the evolution of hydrogen goes higher as the initial hydride wt% increases. Only one peak is shown in the case of the small initial hydride wt%. But two peaks appeared with increasing initial hydride wt%. The activation energies obtained by the first and second peaks are 113.0 and 99.5 kJ/mol respectively. The two site occupation model by Darriet et al. was proved. The influence of HCS on the hydrogen occupation site of Mg2Ni alloy is nonexistent.

  17. Hydrogen absorption-desorption properties of UZr0.29 alloy

    Shuai Maobing; Su Yongjun; Wang Zhenhong; Zhang Yitao

    2001-01-01

    Hydrogen absorption-desorption properties of UZr 0.29 alloy are investigated in detail at hydrogen pressures up to 0.4 MPa and over the temperature range of 300 to 723 K. It absorbs hydrogen up to 2.3 H atoms per F.U. (formula unit) by only one-step reaction and hence each desorption isotherm has a single plateau over nearly the whole hydrogen composition range. The enthalpy and entropy changes of the dissociation reaction are of -78.9 kJ·mol -1 H 2 and 205.3 J·(K·mol H 2 ) -1 , respectively. The alloy shows high durability against powdering upon hydrogenation and may have good heat conductivity. It is predicted that UZr 0.29 alloy may be a suitable material for tritium treatment and storage

  18. Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

    Kitagawa, Yuta; Tanabe, Katsuaki

    2018-05-01

    Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

  19. Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

    Matović Ljiljana Lj.

    2008-01-01

    Full Text Available To study the influence of 3d transition metal addition on desorption kinetics of MgH2 ball milling of MgH2-Co blends was performed under Ar. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behavior is correlated with the dispersion of the metal additive particles on hydride matrix. The activation energy for H2 desorption from MgH2-Co composite was calculated from both non-isothermal and isothermal methods to be 130 kJ/mol which means that mutually diffusion and nucleation and growth of new phase control the dehydration process.

  20. Reactive Desorption of CO Hydrogenation Products under Cold Pre-stellar Core Conditions

    Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

    2018-02-01

    The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as ∼10‑8–10‑9 n H, contradicts the generally accepted idea that at 10 K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO–H2CO–CH3OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H2CO and CH3OH. We find that for temperatures in the range of 10 to 14 K, an upper limit of 0.24 ± 0.02 for the overall elemental carbon loss upon CO conversion into CH3OH. This corresponds with an effective reaction desorption fraction of ≤0.07 per hydrogenation step, or ≤0.02 per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed.

  1. Study of the chemisorption and hydrogenation of propylene on platinum by temperature-programed desorption

    Tsuchiya, S.; Nakamura, M.; Yoshioka, N.

    1978-01-01

    Temperature-programed desorption (TPD) chromotograms of propylene adsorbed on platinum black in the absence or presence of hydrogen preadsorbed, admitted simultaneously, or admitted later, all showed four peaks at about 260/sup 0/ (A), 380/sup 0/ (B), 570/sup 0/ (C), and higher than 720/sup 0/K (D). Peaks A and B were identified as mixtures of propylene and propane, and peaks C and D were methane formed by thermal decomposition of the chemisorbed propylene during desorption. When nitrogen rather than helium was used as the carrier gas for the TPD, only delta-hydrogen was observed; this suggested that propylene was more strongly adsorbed on the platinum than hydrogen. Studies of the reactivities with propylene of the various types of chemisorbed hydrogen previously detected by TPD showed that propylene reacted with ..gamma..-hydrogen present on the surface in the form of hydrogen atoms chemisorbed on top of platinum atoms and with ..beta..-hydrogen, molecular hydrogen chemisorbed in a bridged form, but did not react with delta-hydrogen. Tables and graph.

  2. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  3. Hydrogen absorption/desorption characteristics of room temperature ...

    ZrMn2-Ni system; metal hydrides; hydrogen storage materials. ... where ∼ 2.5 to 2.9 H/F.U. can be reversibly stored under the ideal operating conditions. ... these are promising candidates for stationary and short range mobile applications.

  4. Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts

    Anderson, J.R.; Foger, K.; Breakspere, R.J.

    1979-05-01

    Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts was studied with 0.9-3Vertical Bar3< platinum on silica gel, aerosil, sodium and lanthanum Y zeolites, and ..gamma..-alumina, and on aerosil-supported gold-platinum alloys containing 2, 10, 24, 33, and 85Vertical Bar3< gold. Surface enrichment with gold in the alloy systems, as derived from hydrogen adsorption data and predicted from surface enrichment theory and electron microscopic measurements of particle size, were in good agreement, which indicated that equilibrium was achieved by the thermal treatment (oxygen at 573/sup 0/K, hydrogen at 620/sup 0/K, repeated cycles) used. Hydrogen spillover to gold was observed at the higher hydrogen pressures tested on the alloys with high gold content, and to the zeolite supports. The temperature-programed desorption profiles were independent of gold content, which indicated that gold acts only as diluent, and that isolated surface platinum atoms become populated with hydrogen atoms either by hydrogen atom spillover from platinum ensembles to gold and from the gold to the isolated platinum, and/or by adsorption of a molecule directly on the isolated platinum and chemisorption of one H atom at an adjacent gold atom. The distribution of surface platinum ensembles was evaluated by a computer simulation method.

  5. Adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts

    Etherton, B.P.

    1980-01-01

    The adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts which were examined by a scanning transmission electron microscope (STEM). The metal particle size and number of particles per area of catalyst increased with increasing metal loading. The particles were approx. 10 A. in diameter, cubo-octahedral shaped, and approx. 80-90% disperse. The STEM electron beam caused negligible damage to the samples. Hydrogen adsorption measurements showed that the hydrogen-iridium atom ratio was 1.2:1-1.3:1 and increased with decreasing metal loading. Temperature-programed desorption showed four types of adsorbed hydrogen desorbing at -90/sup 0/C (I), 15/sup 0/C (IV), 115/sup 0/C (II), and 245/sup 0/C (III). Types II and IV desorb from single atom sites and Types I and III from multiple atom sites. Type I is in rapid equilibrium with the gas phase. All desorption processes appear to be first order. Carbon monoxide adsorbed nondissociatively at 25/sup 0/C with approx. 0.7:1 CO/Ir atom ratio. It adsorbed primarily in linear forms at low coverage, but a bridged form appeared at high coverage.

  6. Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

    Li, Ming; Kang, Zhan; Huang, Xiaobo

    2015-01-01

    Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials

  7. Hydrogen desorption properties of MgH2–Ni–Ni2Si composites prepared by mechanochemical method

    Shimada, Motoki; Higuchi, Eiji; Inoue, Hiroshi

    2013-01-01

    Highlights: ► The MgH 2 –Ni composite showed fast hydrogen desorption rate at 250 °C. ► The MgH 2 –Ni–Ni 2 Si composite showed fast hydrogen desorption rate at 220 °C. ► Nanocrystalline Mg 2 Ni and Mg 2 Si were formed between Mg and adjacent Ni or Si. ► Ni 2 Si did not form any alloys and work as a catalyst. -- Abstract: To improve hydrogen desorbability of Mg, some composites were prepared from MgH 2 , Ni and Ni 2 Si mixed powders by the mechanochemical method. The MgH 2 –Ni(2 mol%)–Ni 2 Si(1 mol%) composite was slower in hydrogen desorption rate at 250 °C than the MgH 2 –Ni(2 mol%) composite, while the hydrogen desorption rate at 220 °C for the former was faster than that for the latter. The XRD pattern of the MgH 2 –Ni(2 mol%) composite showed that after hydrogen desorption at 400 °C small diffraction peaks assigned to Mg 2 Ni were observed with peaks assigned to Mg. They shifted to smaller angles after hydrogen absorption at 250 °C and come back to the original positions after hydrogen desorption at 250 °C, suggesting reversible hydrogen absorption/desorption of Mg 2 Ni. In contrast, Ni 2 Si was not changed over the whole processes. These results indicated that Ni 2 Si worked as a catalyst for hydrogen desorption, leading to the improvement of desorbability at 220 °C

  8. Improved hydrogen absorption and desorption kinetics of magnesium-based alloy via addition of yttrium

    Yang, Tai; Li, Qiang; Liu, Ning; Liang, Chunyong; Yin, Fuxing; Zhang, Yanghuan

    2018-02-01

    Yttrium (Y) is selected to modify the microstructure of magnesium (Mg) to improve the hydrogen storage performance. Thereby, binary alloys with the nominal compositions of Mg24Yx (x = 1-5) are fabricated by inexpensive casting technique. Their microstructure and phase transformation during hydriding and dehydriding process are characterized by using X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy analysis. The isothermal hydrogen absorption and desorption kinetics are also measured by a Sievert's-type apparatus at various temperatures. Typical multiphase structures of binary alloy can be clearly observed. All of these alloys can reversibly absorb and desorb large amount of hydrogen at proper temperatures. The addition of Y markedly promotes the hydrogen absorption kinetics. However, it results in a reduction of reversible hydrogen storage capacity. A maximum value of dehydrogenation rate is observed with the increase of Y content. The Mg24Y3 alloy has the optimal desorption kinetic performance, and it can desorb about 5.4 wt% of hydrogen at 380 °C within 12 min. Combining Johnson-Mehl-Avrami kinetic model and Arrhenius equation, the dehydrogenation activation energy of the alloys are evaluated. The Mg24Y3 alloy also has the lowest dehydrogenation activation energy (119 kJ mol-1).

  9. Changes of structural and hydrogen desorption properties of MgH2 indused by ion irradiation

    Kurko Sandra V.

    2010-01-01

    Full Text Available Changes in structural and hydrogen desorption properties of MgH2 induced by ion irradiation have been investigated. MgH2 powder samples have been irradiated with 45 keV B3+ and 120 keV Ar8+ions, with ion fluence of 1015 ions/cm2. The effects of ion irradiation are estimated by numerical calculations using SRIM package. The induced material modifications and their consequences on hydrogen dynamics in the system are investigated by XRD, particle size distribution and TPD techniques. Changes of TPD spectra with irradiation conditions suggest that there are several mechanisms involved in desorption process which depend on defect concentration and their interaction and ordering. The results confirmed that the near-surface area of MgH2 and formation of a substoichiometric MgHx (x<2 play a crucial role in hydrogen kinetics and that various concentrations of induced defects substantially influence H diffusion and desorption kinetics in MgH2. The results also confirm that there is possibility to control the thermodynamic parameters by controlling vacancies concentration in the system.

  10. Effects of Molybdenum Addition on Hydrogen Desorption of TiC Precipitation-Hardened Steel

    Song, Eun Ju; Baek, Seung-Wook; Nahm, Seung Hoon; Suh, Dong-Woo

    2018-03-01

    The hydrogen-trap states in TiC and MoC that have coherent interfaces with ferrite were investigated using first-principles calculation. The trapping sites of TiC were the interfaces and interstitial sites of ferrite. On the other hand, the trapping sites of MoC were ferrite interstitial sites; the interface had a negative binding energy with H. Thermal desorption analysis confirms that the amounts of diffusible hydrogen were significantly reduced by addition of Mo in Ti-bearing steel.

  11. High stability of palladium/kieselguhr composites during absorption/desorption cycling for hydrogen isotope separation

    Lei, Yang, E-mail: lei.y@outlook.com; Liu, Xiaopeng; Li, Shuo; Jiang, Lijun; Zhang, Chao; Li, Shuai; He, Di; Wang, Shumao

    2016-12-15

    Highlights: • Pd/K composites with as high as 57 wt.% of Pd have been successfully prepared. • Palladium particles can be effectively packed into the pores of kieselguhr substrates. • Variation of heat-treatment temperatures hardly affect hydrogen absorption capacity and hydrogen saturation time of the Pd/K. • Anti-pulverization property of Pd/K can be improved by packing palladium into the kieselguhr internal pores and heating at 1300 °C. - Abstract: Palladium/kieselguhr (Pd/K) composites with 57 wt.% of Pd were prepared by an improved dipping and thermal decomposition method and heated at elevated temperature to reduce breakdown during hydrogenation-dehydrogenation cycles. The hydrogen absorption kinetic properties of the samples heated at different temperatures were tested under the condition of 20 °C with 100 kPa hydrogen pressure. The 1300 °C heated Pd/K composites were repeated up to 4010 absorption and desorption cycles at temperature ranges between −40 °C and 200 °C. The results show that the phase structure, hydrogen absorption capacity and hydrogen saturation time of the Pd/K were not affected by the change of heat-treated temperatures. And after heat treatment at 1300 °C, the Pd/K particles were strengthened and fraction of larger than 80 mesh were as high as 93.4%.

  12. Preparation and Hydrogen Absorption/Desorption of Nanoporous Palladium Thin Films

    Wen-Chung Li

    2009-12-01

    Full Text Available Nanoporous Pd (np-Pd was prepared by co-sputtering Pd-Ni alloy films onto Si substrates, followed by chemical dealloying with sulfuric acid. X-ray diffractometry and chemical analysis were used to track the extent of dealloying. The np-Pd structure was changed from particle-like to sponge-like by diluting the sulfuric acid etchant. Using suitable precursor alloy composition and dealloying conditions, np-Pd films were prepared with uniform and open sponge-like structures, with interconnected ligaments and no cracks, yielding a large amount of surface area for reactions with hydrogen. Np-Pd films exhibited shorter response time for hydrogen absorption/desorption than dense Pd films, showing promise for hydrogen sensing.

  13. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  14. Desorption of hydrogen from magnesium hydride: in-situ electron diffraction study

    Paik, B.; Jones, I.P.; Walton, A.; Mann, V.; Book, D.; Harris, I.R.

    2009-01-01

    The dynamics of a phase change has been studied where electron beam in Transmission Electron Microscope (TEM) has been used to transform MgH 2 into magnesium. A combination of in-situ Electron Diffraction (ED) and an in-situ Electron Energy Loss Spectroscopy (EELS) study under ED mode describes the phase transformation in terms of, respectively, change in the crystal structure and Plasmon energy shift. The orientation relation [001] MgH2 //[-2110] Mg and (-110) MgH2 //(0001) Mg , obtained from the ED study, has been used to propose a model for the movements of magnesium atoms in the structural change to describe the dynamics of the process. The in-situ EELS study has been compared with the existing H-desorption model. The study aims to describe the sorption dynamics of hydrogen in MgH 2 which is a base material for a number of promising hydrogen storage systems. (author)

  15. Measurement of hydrogen solubility and desorption rate in V-4Cr-4Ti and liquid lithium-calcium alloys

    Park, J.H.; Erck, R.; Park, E.T. [Argonne National Lab., IL (United States)] [and others

    1997-04-01

    Hydrogen solubility in V-4Cr-4Ti and liquid lithium-calcium was measured at a hydrogen pressure of 9.09 x 10{sup {minus}4} torr at temperatures between 250 and 700{degrees}C. Hydrogen solubility in V-4Cr-4Ti and liquid lithium decreased with temperature. The measured desorption rate of hydrogen in V-4Cr-4Ti is a thermally activated process; the activation energy is 0.067 eV. Oxygen-charged V-4Cr-4Ti specimens were also investigated to determine the effect of oxygen impurity on hydrogen solubility and desorption in the alloy. Oxygen in V-4Cr-4Ti increases hydrogen solubility and desorption kinetics. To determine the effect of a calcium oxide insulator coating on V-4Cr-4Ti, hydrogen solubility in lithium-calcium alloys that contained 0-8.0 percent calcium was also measured. The distribution ratio R of hydrogen between liquid lithium or lithium-calcium and V-4Cr-4Ti increased as temperature decreased (R {approx} 10 and 100 at 700 and 250{degrees}C, respectively). However at <267{degrees}C, solubility data could not be obtained by this method because of the slow kinetics of hydrogen permeation through the vanadium alloy.

  16. Measurement of hydrogen solubility and desorption rate in V-4Cr-4Ti and liquid lithium-calcium alloys

    Park, J.H.; Erck, R.; Park, E.T.

    1997-01-01

    Hydrogen solubility in V-4Cr-4Ti and liquid lithium-calcium was measured at a hydrogen pressure of 9.09 x 10 -4 torr at temperatures between 250 and 700 degrees C. Hydrogen solubility in V-4Cr-4Ti and liquid lithium decreased with temperature. The measured desorption rate of hydrogen in V-4Cr-4Ti is a thermally activated process; the activation energy is 0.067 eV. Oxygen-charged V-4Cr-4Ti specimens were also investigated to determine the effect of oxygen impurity on hydrogen solubility and desorption in the alloy. Oxygen in V-4Cr-4Ti increases hydrogen solubility and desorption kinetics. To determine the effect of a calcium oxide insulator coating on V-4Cr-4Ti, hydrogen solubility in lithium-calcium alloys that contained 0-8.0 percent calcium was also measured. The distribution ratio R of hydrogen between liquid lithium or lithium-calcium and V-4Cr-4Ti increased as temperature decreased (R ∼ 10 and 100 at 700 and 250 degrees C, respectively). However at <267 degrees C, solubility data could not be obtained by this method because of the slow kinetics of hydrogen permeation through the vanadium alloy

  17. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  18. Analysis of the technique Thermal Desorption Spectroscopy (TDS) and its Application for the Characterization of Metal -Hydrogen Systems

    Castro, F.J.

    2000-01-01

    We present the theoretical and experimental developments made to study the desorption of hydrogen from metallic samples by Thermal Desorption Spectroscopy (TDS). With this technique gas desorption is stimulated by the programmed heating of the sample. To perform the study we set up a newly designed equipment and develop theoretical models of the kinetic processes involved. The equipment and the models are used to analyze the desorption process in a real system. We begin by analyzing the models developed to interpret the results of the experiments. These models consider simultaneously bulk diffusion and surface reaction processes in metal-hydrogen systems with one or two thermodynamic phases. We present numerical results, computer simulations and analytical approximations of the original models. Based on these results we analyze the main features of the spectra for the different relevant kinetic processes, and determine the changes induced in them when material parameters (activation energies, geometry) or experimental parameters (heating speed, initial concentration) are modified.We present the original equipment, designed and constructed during this work to perform the TDS experiments. We describe its main characteristics, its components, its range of operation and its sensibility. We also offer an analysis of the background spectrum. We use the Pd-H system to test the equipment and the models. The samples chosen, powders, granules, foils and wires, were previously characterized to analyze their composition, their morphology and their characteristic size. We show the results of Scanning Electron Microscopy (SEM) observation, X ray diffraction (XRD) and Auger Electron Spectroscopy (AES) analysis.We then present and analyze in depth the experimental desorption spectra of the palladium powder. Based on the analysis we determine the rate limiting step for desorption and the characteristic activation energies. When the system is on the b phase (hydride) the rate

  19. Analysis of hydrogen distribution on Mg-Ni alloy surface by scanning electron-stimulated desorption ion microscope (SESDIM)

    Yamaga, Atsushi; Hibino, Kiyohide; Suzuki, Masanori; Yamada, Masaaki; Tanaka, Kazuhide; Ueda, Kazuyuki

    2008-01-01

    Hydrogen distribution and behavior on a Mg-Ni alloy surface are studied by using a time-of-flight electron-stimulated desorption (TOF-ESD) microscopy and a scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDX). The desorbed hydrogen ions are energy-discriminated and distinguished into two characters in the adsorbed states, which belong to Mg 2 Ni grains and the other to oxygen-contaminated Mg phase at the grain boundaries. Adsorbed hydrogen is found to be stable up to 150 deg. C, but becomes thermally unstable around at 200 deg. C

  20. Molecular Beam-Thermal Desorption Spectrometry (MB-TDS Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes

    Jorge H. F. Ribeiro

    2012-02-01

    Full Text Available Different types of experimental studies are performed using the hydrogen storage alloy (HSA MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal, chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC. The recently developed molecular beam—thermal desorption spectrometry (MB-TDS technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA, and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

  1. Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes.

    Lobo, Rui F M; Santos, Diogo M F; Sequeira, Cesar A C; Ribeiro, Jorge H F

    2012-02-06

    Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi 3.6 Co 0.85 Al 0.3 Mn 0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam-thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

  2. The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry

    Ellis, Wade C.; Lewis, Charlotte R.; Openshaw, Anna P.; Farnsworth, Paul B.

    2016-09-01

    We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

  3. Desorption process of hydrogen starting from the Mg2NiH4 and Mg2NiH0.3

    Iturbe G, J.L.; Basurto S, R.; Lopez M, B.E.

    2002-01-01

    In this work the desorption velocity of H 2 was determined starting from the magnesium nickel hydride once the reaction between the intermetallic and the hydrogen was realized, the compound were analysed by means of a thermogravimetric equipment, the conditions for carrying out the analysis were: 10 C by minute in nitrogen atmosphere at a volume of 50 ml by minute, subsequently the isotherms at different times were programmed and the desorption velocity of hydrogen was determined. The results show that the desorption velocity of hydrogen depends of the temperature, using only the nitrogen flux which acts as a carrier gas. Observing that the hydrogen liberation is carried out by means of two mechanisms according to the isotherms obtained. (Author)

  4. Hydrogen isotope inventory in the graphite divertor tiles of ASDEX Upgrade as measured by thermal desorption spectroscopy

    Franzen, P.; Behrisch, R.; Garcia-Rosales, C.; Schleussner, D.; Roesler, D.; Becker, J.; Knapp, W.; Edelmann, C.

    1997-01-01

    The hydrogen and deuterium inventories of the ASDEX Upgrade divertor tiles were measured after the experimental period from December 1994 to July 1995 by thermal desorption spectroscopy (TDS) of samples cut out of the divertor tiles. The samples were heated by electron bombardment up to 2100 K; the released gases were measured by means of a calibrated quadrupole mass spectrometer. The measured hydrogen or deuterium inventories are of the order of 10 23 m -2 . They are larger for samples of the inner divertor than of the outer divertor by a factor of about 2. The largest inventory was found at the separatrix position of the inner divertor. Most of the released hydrogen (H) can be attributed to water adsorbed in the near surface region during the air exposure prior to the TDS measurements. The total inventories measured by TDS exceed the inventories in the near surface region (< 25 μm) measured by ion beam analysis methods by a factor of up to 10. Hence, the total hydrogen retention is governed by the diffusion out of the near surface region deep into the material. The hydrogen and deuterium inventories decreased with increasing surface temperature. (author). 64 refs, 12 figs, 2 tabs

  5. Hydrogen spillover phenomenon: Enhanced reversible hydrogen adsorption/desorption at Ta{sub 2}O{sub 5}-coated Pt electrode in acidic media

    Sata, Shunsuke [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Awad, Mohamed I.; El-Deab, Mohamed S. [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Department of Chemistry, Faculty of Science, Cairo University, Cairo (Egypt); Okajima, Takeyoshi [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-04-01

    The current study is concerned with the preparation and characterization of tantalum oxide-loaded Pt (TaO{sub x}/Pt) electrodes for hydrogen spillover application. XPS, SEM, EDX and XRD techniques are used to characterize the TaO{sub x}/Pt surfaces. TaO{sub x}/Pt electrodes were prepared by galvanostatic electrodeposition of Ta on Pt from LiF-NaF (60:40 mol%) molten salts containing K{sub 2}TaF{sub 7} (20 wt%) at 800 deg. C and then by annealing in air at various temperatures (200, 400 and 600 deg. C). The thus-fabricated TaO{sub x}/Pt electrodes were compared with the non-annealed Ta/Pt and the unmodified Pt electrodes for the hydrogen adsorption/desorption (H{sub ads}/H{sub des}) reaction. The oxidation of Ta to the stoichiometric oxide (Ta{sub 2}O{sub 5}) increases with increasing the annealing temperature as revealed from XPS and X-ray diffraction (XRD) measurements. The higher the annealing temperature the larger is the enhancement in the H{sub ads}/H{sub des} reaction at TaO{sub x}/Pt electrode. The extraordinary increase in the hydrogen adsorption/desorption at the electrode annealed at 600 deg. C is explained on the basis of a hydrogen spillover-reverse spillover mechanism. The hydrogen adsorption at the TaO{sub x}/Pt electrode is a diffusion-controlled process.

  6. Hydrogen adsorption and desorption in carbon nanotube systems and its mechanisms

    Shiraishi, M.; Takenobu, T.; Ata, M. [Materials Laboratories, SONY Corporation, Shin-Sakuragaoka 2-1-1, Hodogaya-ku, 240-0036, Yokohama (Japan); Kataura, H. [Department of Physics, Faculty of Science, Tokyo Metropolitan University, Minami-Osawa, Hachioji, 192-0397, Tokyo (Japan)

    2004-04-01

    The hydrogen physisorption properties in single-walled carbon nanotube (SWNT) based materials were characterized. The SWNTs were highly purified and three useful pores for hydrogen physisorption were activated. Hydrogen was physisorbed in intra-tube pores at room temperature and the capacity was estimated to be about 0.3-0.4 wt. % at room temperature. The adsorption capacity can be explained by the Langmuir model. The intra-tube pores have large adsorption potential and this induces hydrogen physisorption at comparatively higher temperatures. This fact indicates the importance of fabricating sub-nanometer ordered pores for this phenomena. (orig.)

  7. Actuation of Pneumatic Artificial Muscle via Hydrogen Absorption/Desorption of Metal Hydride-LaNi5

    Thanana Nuchkrua

    2015-01-01

    Full Text Available This paper presents experimental studies on mechanical actuations of a pneumatic artificial muscle (PAM, which is driven by hydrogen gas based metal hydride (MH. The dynamic performances of hydrogen absorption/desorption, taking place within a MH reactor, are controlled via implementing cooling/heating effects of a thermoelectric module (TEM. Hydrogen pressure is applied as a driving force to commanding work outputs of the PAM as desired mechanical actuations. Due to strong inherent nonlinearity, a conventional proportional integral derivative (PID control law is not capable of regulating thermodynamic variables of the HM reaction according to desired performances of the PAM. In this study, the fuzzy adaptive PID control is proposed in manipulating the MH reaction via the TEM. This viability of the proposed methodology is confirmed by the fact that the gains of PID control law are adapted by fuzzy rule-based tuning scheme at various operating conditions of the MH reactor. The experimental results show that the proposed control technique is much more effective than a PID control in both transient and steady state performances of the MH reactor for servo mechanical actuation of the PAM.

  8. Reduction of hydrogen desorption temperature of ball-milled MgH2 by NbF5 addition

    Recham, N.; Bhat, V.V.; Kandavel, M.; Aymard, L.; Tarascon, J.-M.; Rougier, A.

    2008-01-01

    Enhanced sorption properties of ball-milled MgH 2 are reported by adding NbF 5 . Among various catalyst amounts, 2 mol% of NbF 5 reveals to be the optimum concentration leading to significant reduction of the desorption temperature as well as faster kinetics of ball-milled MgH 2 . At 200 deg. C, temperature at which MgH 2 does not show any activity, MgH 2NbF 5 /2mol% composite desorbs 3.2 wt.% of H 2 in 50 mins. Interestingly, the addition of NbF 5 is also associated with an increase in the desorption pressure. At 300 deg. C, MgH 2NbF 5 /2mol% composite starts to desorb hydrogen at 600 mbar in comparison with 1 mbar for MgH 2 . Further improvements were successfully achieved by pre-grinding NbF 5 prior to ball-milling the catalyst with MgH 2 . Such pre-ground NbF 5 catalyzed MgH 2 composite desorbs 3 wt.% of H 2 at 150 deg. C. Improved properties are associated with smaller activation energies down to values close to the enthalpy of formation of MgH 2 . Finally, the mechanism at the origin of the enhancement is discussed in terms of catalyst stability, MgF 2 formation and electronic density localization

  9. Acidophilic sulfur disproportionation

    Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

    2013-07-01

    Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

  10. Catalytic effect of Ni, Mg2Ni and Mg2NiH4 upon hydrogen desorption from MgH2

    Čermák, Jiří; David, Bohumil

    2011-01-01

    Roč. 36, č. 21 (2011), s. 13614-13620 ISSN 0360-3199 R&D Projects: GA ČR GA106/09/0814; GA ČR(CZ) GAP108/11/0148 Institutional research plan: CEZ:AV0Z20410507 Keywords : MgH2 * Hydrogen storage * Hydrogen desorption * Catalysis Subject RIV: JG - Metallurgy Impact factor: 4.054, year: 2011

  11. Thermoanalytical investigation of the hydrogen absorption behaviour of Sm2Fe17-xGax at high hydrogen pressures

    Handstein, A.; Kubis, M.; Gebel, B.; Mueller, K.-H.; Schultz, L.; Gutfleisch, O.; Harris, I.R.; Birmingham Univ.

    1998-01-01

    The complete disproportionation of Sm 2 Fe 17-x Ga x during annealing in hydrogen is hindered due to an increased stability of the compounds with a higher Ga content (x ≥ 1). Therefore the HD process as the first step of HDDR (hydrogenation-disproportionation-desorption-recombination) has to be carried out at a high hydrogen pressure for x ≥ 1. The hydrogen absorption behaviour of Sm 2 Fe 17-x Ga x (x = 0, 0.5, 1 and 2) was investigated by means of hydrogen differential thermal analysis (HDTA) and high pressure differential scanning calorimetry (HPDSC) at hydrogen pressures up to 70 bar. A dependency of hydrogenation and disproportionation temperatures on hydrogen pressure and Ga content was found. The comparison with other substituents (M = Al and Si) instead of M = Ga showed an increased stability of Sm 2 Fe 17-x M x compounds against disproportionation by hydrogen in the sequence Al, Ga and Si. The Curie temperatures of the interstitially hydrogenated Th 2 Zn 17 -type materials increase with the hydrogen pressure. In order to produce coercive and thermally stable Sm 2 Fe 15 Ga 2 C y powder by means of the HDDR process, we recombined material disproportionated at different hydrogen pressures. Preliminary results of magnetic properties of this HDDR treated and gas-carburized Sm 2 Fe 15 Ga 2 C y are discussed. (orig.)

  12. The kinetics of hydrogen absorption/desorption within nanostructured composite Ni79.1Co18.6Cu2.3 alloy using resistometry

    Spasojević, M.; Maričić, A.; Ribić Zelenović, L.; Krstajić, N.; Spasojević, P.

    2013-01-01

    Highlights: ► Nanostructured Ni 79.1 Co 18.6 Cu 2.3 powder was obtained by electrochemical deposition. ► Correlation observed between electrical conductivity and absorbed hydrogen amount. ► Hydrogen absorption/desorption mechanism was determined. - Abstract: Ni 79.1 Co 18.6 Cu 2.3 powder was obtained by electrochemical deposition from an ammonium sulfate bath. The structure and surface morphology of the powder were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemically obtained Ni 79.1 Co 18.6 Cu 2.3 alloy contained an amorphous phase and nanocrystals with an average size of 6.8 nm of FCC phase of the solid solution of cobalt and copper in nickel. Nanocrystals were characterized by a high average microstrain value and high minimum density of chaotically distributed dislocations. X-ray analysis also showed that powder hydrogenation at an elevated temperature of up to 200 °C did not change unit cell parameters and mean crystallite size value. SEM images show the formation of two shapes of powder particles: large cauliflower-like particles and small dendritic ones. Powder pressing at 10 MPa and at 25 °C gave samples that were analyzed for hydrogen absorption/desorption within the temperature range of 160–200 °C. Changes in electrical resistivity during absorption/desorption were monitored. The reciprocal value of resistivity (electrical conductivity) was found to increase linearly with increasing amount of absorbed hydrogen. The experimental results were used to propose an absorption/desorption mechanism. The adsorbed hydrogen molecule dissociates on alloy surface, forming adsorbed atoms. Adatoms penetrate and diffuse into the bulk of the alloy, simultaneously donating their electrons to the conduction band of the alloy. The increase in the concentration of free electrons induces a decrease in electrical resistivity. The overall absorption rate during initial absorption is determined by the

  13. Statistical physics modeling of hydrogen desorption from LaNi{sub 4.75}Fe{sub 0.25}: Stereographic and energetic interpretations

    Wjihi, Sarra [Unité de Recherche de Physique Quantique, 11 ES 54, Faculté des Science de Monastir (Tunisia); Dhaou, Houcine [Laboratoire des Etudes des Systèmes Thermiques et Energétiques (LESTE), ENIM, Route de Kairouan, 5019 Monastir (Tunisia); Yahia, Manel Ben; Knani, Salah [Unité de Recherche de Physique Quantique, 11 ES 54, Faculté des Science de Monastir (Tunisia); Jemni, Abdelmajid [Laboratoire des Etudes des Systèmes Thermiques et Energétiques (LESTE), ENIM, Route de Kairouan, 5019 Monastir (Tunisia); Lamine, Abdelmottaleb Ben, E-mail: abdelmottaleb.benlamine@gmail.com [Unité de Recherche de Physique Quantique, 11 ES 54, Faculté des Science de Monastir (Tunisia)

    2015-12-15

    Statistical physics treatment is used to study the desorption of hydrogen on LaNi{sub 4.75}Fe{sub 0.25}, in order to obtain new physicochemical interpretations at the molecular level. Experimental desorption isotherms of hydrogen on LaNi{sub 4.75}Fe{sub 0.25} are fitted at three temperatures (293 K, 303 K and 313 K), using a monolayer desorption model. Six parameters of the model are fitted, namely the number of molecules per site n{sub α} and n{sub β}, the receptor site densities N{sub αM} and N{sub βM}, and the energetic parameters P{sub α} and P{sub β}. The behaviors of these parameters are discussed in relationship with desorption process. A dynamic study of the α and β phases in the desorption process was then carried out. Finally, the different thermodynamical potential functions are derived by statistical physics calculations from our adopted model.

  14. Microbiological disproportionation of inorganic sulfur compounds

    Finster, Kai

    2008-01-01

    The disproportionation of inorganic sulfur intermediates at moderate temperatures (0-80 °C) is a microbiologically catalyzed chemolithotrophic process in which compounds like elemental sulfur, thiosulfate, and sulfite serve as both electron donor and acceptor, and generate hydrogen sulfide and su...

  15. Electron beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in-situ electron beam induced desorption

    Olynick, D.L.; Cord, B.; Schipotinin, A.; Ogletree, D.F.; Schuck, P.J.

    2009-11-13

    Hydrogen Silsesquioxane (HSQ) is used as a high-resolution resist with resolution down below 10nm half-pitch. This material or materials with related functionalities could have widespread impact in nanolithography and nanoscience applications if the exposure mechanism was understood and instabilities controlled. Here we have directly investigated the exposure mechanism using vibrational spectroscopy (both Raman and Fourier transform Infrared) and electron beam desorption spectrocscopy (EBDS). In the non-networked HSQ system, silicon atoms sit at the corners of a cubic structure. Each silicon is bonded to a hydrogen atom and bridges 3 oxygen atoms (formula: HSiO3/2). For the first time, we have shown, via changes in the Si-H2 peak at ~;;2200 cm -1 in the Raman spectra and the release of SiHx products in EBID, that electron-bam exposed materials crosslinks via a redistribution reaction. In addition, we observe the release of significantly more H2 than SiH2 during EBID, which is indicative of additional reaction mechanisms. Additionally, we compare the behavior of HSQ in response to both thermal and electron-beam induced reactions.

  16. High hydrogen desorption properties of Mg-based nanocomposite at moderate temperatures: The effects of multiple catalysts in situ formed by adding nickel sulfides/graphene

    Xie, Xiubo; Chen, Ming; Liu, Peng; Shang, Jiaxiang; Liu, Tong

    2017-12-01

    Nickel sulfides decorated reduced graphene oxide (rGO) has been produced by co-reducing Ni2+ and graphene oxide (GO), and is subsequently ball milled with Mg nanoparticles (NPs) produced by hydrogen plasma metal reaction (HPMR). The nickel sulfides of about 800 nm completely in situ change to MgS, Mg2Ni and Ni multiple catalysts after first hydrogenation/dehydrogenation process at 673 K. The Mg-5wt%NiS/rGO nanocomposite shows the highest hydrogen desorption kinetics and capacity properties, and the catalytic effect order of the additives is NiS/rGO, NiS and rGO. At 573 K, the Mg-NiS/rGO nanocomposite can quickly desorb 3.7 wt% H2 in 10 min and 4.5 wt% H2 in 60 min. The apparent hydrogen absorption and desorption activation energies of the Mg-5wt%NiS/rGO nanocomposite are decreased to 44.47 and 63.02 kJ mol-1, smaller than those of the Mg-5wt%rGO and Mg-5wt%NiS samples. The best hydrogen desorption properties of the Mg-5wt%NiS/rGO nanocomposite can be explained by the synergistic catalytic effects of the highly dispersed MgS, Mg2Ni and Ni catalysts on the rGO sheets, and the more nucleation sites between the catalysts, rGO sheets and Mg matrix.

  17. Hydrogen absorption/desorption properties in the TiCrV based alloys

    A. Martínez

    2012-10-01

    Full Text Available Three different Ti-based alloys with bcc structure and Laves phase were studied. The TiCr1.1V0.9, TiCr1.1V0.45Nb0.45 and TiCr1.1V0.9 + 4%Zr7Ni10 alloys were melted in arc furnace under argon atmosphere. The hydrogen absorption capacity was measured by using aparatus type Sievert's. Crystal structures, and the lattice parameters were determined by using X-ray diffraction, XRD. Microestructural analysis was performed by scanning electron microscope, SEM and electron dispersive X-ray, EDS. The hydrogen storage capacity attained a value of 3.6 wt. (% for TiCr1.1V0.9 alloy in a time of 9 minutes, 3.3 wt. (% for TiCr1.1V0.45Nb0.45 alloy in a time of 7 minutes and 3.6 wt. (% TiCr1.1V0.9 + 4%Zr7Ni10 with an increase of the hydrogen absorption kinetics attained in 2 minutes. This indicates that the addition of Nb and 4%Zr7Ni10 to the TiCrV alloy acts as catalysts to accelerate the hydrogen absorption kinetics.

  18. Beneficial effect of carbon on hydrogen desorption kinetics from Mg–Ni–In alloy

    Čermák, Jiří; Král, Lubomír

    2013-01-01

    Roč. 546, JAN (2013), s. 129-137 ISSN 0925-8388 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA ČR GA106/09/0814; GA ČR(CZ) GAP108/11/0148 Institutional research plan: CEZ:AV0Z20410507 Keywords : Energy storage materials * Hydrogen absorbing materials * Metal hydrides Subject RIV: JG - Metallurgy Impact factor: 2.726, year: 2013

  19. Carboxylate ligands drastically enhance the rates of oxo exchange and hydrogen peroxide disproportionation by oxo manganese compounds of potential biological significance.

    Dubois, Lionel; Pécaut, Jacques; Charlot, Marie-France; Baffert, Carole; Collomb, Marie-Noëlle; Deronzier, Alain; Latour, Jean-Marc

    2008-01-01

    To mimic the carboxylate-rich active site of the manganese catalases more closely we introduced carboxylate groups into dimanganese complexes in place of nitrogen ligands. The series of dimanganese(III,IV) complexes of tripodal ligands [Mn(2)(L)(2)(O)(2)](3+/+/-/3-) was extended from those of tpa (1) and H(bpg) (2) to those of H(2)(pda) (3) and H(3)(nta) (4) (tpa=tris-picolylamine, H(bpg)=bis-picolylglycylamine, H(2)(pda)=picolyldiglycylamine, H(3)(nta)=nitrilotriacetic acid). While 3 [Mn(2)(pda)(2)(O)(2)][Na(H(2)O)(3)] could be synthesized at -20 degrees C and characterized in the solid state, 4 [Mn(2)(nta)(2)(O)(2)](3-) could be obtained and studied only in solution at -60 degrees C. A new synthetic procedure for the dimanganese(III,III) complexes was devised, using stoichiometric reduction of the dimanganese(III,IV) precursor by the benzil radical with EPR monitoring. This enabled the preparation of the parent dimanganese(III,III) complex 5 [Mn(2)(tpa)(2)(O)(2)](ClO(4))(2), which was structurally characterized. The UV/visible, IR, EPR, magnetic, and electrochemical properties of complexes 1-3 and 5 were analyzed to assess the electronic changes brought about by the carboxylate replacement of pyridine ligands. The kinetics of the oxo ligand exchanges with labeled water was examined in acetonitrile solution. A dramatic effect of the number of carboxylates was evidenced. Interestingly, the influence of the second carboxylate substitution differs from that of the first one probably because this substitution occurs on an out-of-plane coordination while the former occurs in the plane of the [Mn(2)O(2)] core. Indeed, on going from 1 to 3 the exchange rate was increased by a factor of 50. Addition of triethylamine caused a rate increase for 1, but not for 3. The abilities of 1-3 to disproportionate H(2)O(2) were assessed volumetrically. The disproportionation exhibited a sensitivity corresponding to the carboxylate substitution. These observations strongly suggest that

  20. Measurement of solubility of hydrogen isotopes in Li-Pb by adsorption and desorption method

    Edao, Yuki; Katayama, K.; Fukada, S.

    2014-01-01

    Measurement of tritium solubility in lithium lead eutectic alloy (Li-Pb) has been performed under the Japan-US collaboration work of 'TITAN'. The present paper reports that results of H and D solubility in Li-Pb which melted in an alumina tube determined by means of a constant volume method, and also reports an experimental apparatus for measurement of tritium solubility in Li-Pb in a tungsten crucible is improved and examined in the STAR facility of the Idaho National Laboratory. It was shown that H solubility in Li-Pb was easily influenced by impurities, interaction with surrounding materials and evaporated Li-Pb. The influences were suggested to be caused by large scattering among the previously reported data on solubility of hydrogen isotopes in Li-Pb. (author)

  1. Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

    Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

    2018-05-09

    Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

  2. Effects of buffer agents on hydrogen adsorption and desorption at/within activated carbon for the negative electrode of aqueous asymmetric supercapacitors

    Chien, Hsiu-Chuan; Wu, Tzu-Ho; Rajkumar, Muniyandi; Hu, Chi-Chang

    2016-01-01

    Highlights: • H adsorption causes local pH increase and negatively shifts the double-layer potential window. • The local pH variation at AC/electrolyte interface can be controlled via adding buffer agents. • H adsorption potential on AC in buffer electrolytes follows the Nernstian dependence. • The pseudocapacitive reversibility of H adsorption/desorption at/within AC is too poor. - Abstract: In this work, the effects of adding buffer agents into aqueous electrolytes on the hydrogen adsorption/desorption behaviour at/within activated carbon are systematically investigated for the negative electrode of asymmetric supercapacitors. Due to the poor electrochemical reversibility of hydrogen adsorption/desorption at/within activated carbon, the hydrogen responses at/within activated carbon are not suitable for pseudo-capacitive energy storage of high-performance asymmetric supercapacitor. The electrochemical adsorption of H atoms consumes protons and causes the local pH change at the activated carbon/electrolyte interface, leading to the negative shift in the H adsorption potential when weakly acidic, neutral, and weakly basic electrolytes without buffer agents are employed. The addition of buffer agents into electrolytes significantly improves the rate of proton supply and promotes the rate of hydrogen adsorption at/within AC. Interestingly, the onset potential of significant H adsorption obtained from the buffered electrolytes generally follows the Nernstian dependence, suggesting the Nerstian dependence of H"+/H_a_d_s on AC at all pH values. In order to obtain the energy storage devices with high coulombic and energy efficiencies, the onset potential of significant H adsorption obtained from the electrolyte containing buffer agents is a reliable lower potential limit of the AC-coated negative electrode for aqueous asymmetric supercapacitors.

  3. Local stabilization of single-walled carbon nanotubes on Si(100)-2 x 1:H via nanoscale hydrogen desorption with an ultrahigh vacuum scanning tunnelling microscope

    Albrecht, Peter M; Lyding, Joseph W

    2007-01-01

    An ultrahigh vacuum scanning tunnelling microscope (UHV-STM) was used to modify the interface between isolated ∼10 A-diameter single-walled carbon nanotubes (SWNTs) and the hydrogen-passivated Si(100) surface. Room-temperature UHV-STM desorption of hydrogen at the SWNT/H-Si(100) interface resulted in the local mechanical stabilization of tubes originally perturbed by the rastered STM tip under nominal imaging conditions. For the section of the SWNT contacted by depassivated Si, a topographic depression of 1.5 A (1 A) was measured in the case of parallel (nearly perpendicular) alignment between the tube axis and the Si dimer rows, in agreement with existing first-principles calculations. The compatibility of hydrogen-resist UHV-STM nanolithography with SWNTs adsorbed on H-Si(100) would enable the atomically precise placement of single molecules in proximity to the tube for the bottom-up fabrication of molecular electronic devices

  4. Hydrogen storage behavior of ZrCo1-xNix alloys

    Jat, Ram Avtar; Parida, S.C.; Agarwal, Renu; Kulkarni, S.G.

    2012-01-01

    Intermetallic compound ZrCo is proposed as a candidate material for storage, supply and recovery of hydrogen isotopes in International Thermonuclear Experimental Reactor (ITER) Storage and Delivery System (SDS). However, it has been reported that upon repeated hydriding-dehydriding cycles, ZrCo undergoes disproportionation as per the reaction; 2ZrCo + H 2 ↔ ZrH 2 + ZrCO 2 . This results in reduction in hydrogen storage capacity of ZrCo, which is not a desirable property for SDS. Konishi et al. reported that the disproportionation reaction can be suppressed by decreasing the desorption temperature. It is anticipated that suitable ternary alloying of ZrCo can elevated the hydrogen equilibrium pressure and hence decrease the desorption temperature for supply of 100 kPa of hydrogen. In this study, we have investigated the effect of Ni content on the hydrogenation behavior of ZrCo 1-x Ni x alloys

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    U.S. Department of Health & Human Services — Medicaid Disproportionate Share Hospital (DSH) Payments This link provides you with information about Medicaid DSH Payments. You can find information on DSH Audit...

  6. Physicochemical and thermodynamic investigation of hydrogen absorption and desorption in LaNi3.8Al1.0Mn0.2 using the statistical physics modeling

    Bouaziz, Nadia; Ben Manaa, Marwa; Ben Lamine, Abdelmottaleb

    2018-06-01

    In the present work, experimental absorption and desorption isotherms of hydrogen in LaNi3.8Al1.0Mn0.2 metal at two temperatures (T = 433 K, 453 K) have been fitted using a monolayer model with two energies treated by statistical physics formalism by means of the grand canonical ensemble. Six parameters of the model are adjusted, namely the numbers of hydrogen atoms per site nα and nβ, the receptor site densities Nmα and Nmβ, and the energetic parameters Pα and Pβ. The behaviors of these parameters are discussed in relationship with temperature of absorption/desorption process. Then, a dynamic investigation of the simultaneous evolution with pressure of the two α and β phases in the absorption and desorption phenomena using the adjustment parameters. Thanks to the energetic parameters, we calculated the sorption energies which are typically ranged between 276.107 and 310.711 kJ/mol for absorption process and between 277.01 and 310.9 kJ/mol for desorption process comparable to usual chemical bond energies. The calculated thermodynamic parameters such as entropy, Gibbs free energy and internal energy from experimental data showed that the absorption/desorption of hydrogen in LaNi3.8Al1.0Mn0.2 alloy was feasible, spontaneous and exothermic in nature.

  7. Hydrogen absorption-desorption properties of Ti0.32Cr0.43V0.25 alloy

    Cho, Sung-Wook; Shim, Gunchoo; Choi, Good-Sun; Park, Choong-Nyeon; Yoo, Jeong-Hyun; Choi, Jeon

    2007-01-01

    Ti 0.32 Cr 0.43 V 0.25 alloy specimens were heat treated, and its various hydrogen storage properties were measured at 303 K to examine its potential as a hydrogen storage material. The heat treatment improved not only the total and the effective hydrogen storage capacities, but also the plateau flatness. The heat of hydride formation was approximately -36 kJ/mol H 2 . The effective hydrogen storage capacity remained at approximately 2 wt% after 1000 cycles of pressure swing cyclic tests. The hydrogen storage capacity could be recovered almost to the initial state by reactivating the alloy. The hydrogen absorption rate increased with the repetition of cycling for the first several cycles and remained almost constant afterward. At the 504th cycle, more than 98% of the hydrogen was absorbed within the first 2 min. X-ray diffraction (XRD) patterns showed that the crystal structure of the alloy became more amorphous as the number of cycles increased

  8. Data compilation for particle impact desorption

    Oshiyama, Takashi; Nagai, Siro; Ozawa, Kunio; Takeuchi, Fujio.

    1984-05-01

    The desorption of gases from solid surfaces by incident electrons, ions and photons is one of the important processes of hydrogen recycling in the controlled thermonuclear reactors. We have surveyed the literature concerning the particle impact desorption published through 1983 and compiled the data on the desorption cross sections and desorption yields with the aid of a computer. This report presents the results obtained for electron stimulated desorption, the desorption cross sections and yields being given in graphs and tables as functions of incident electron energy, surface temperature and gas exposure. (author)

  9. The kinetics of hydrogen absorption/desorption within nanostructured composite Ni{sub 79.1}Co{sub 18.6}Cu{sub 2.3} alloy using resistometry

    Spasojevic, M., E-mail: ljiljana.spasojevic51@yahoo.com [Joint Laboratory for Advanced Materials of the Serbian Academy of Science and Arts, Section for Amorphous Systems, Svetog Save 65, 32000 Cacak, Republic of Serbia (Serbia); Faculty of Agronomy Cacak, University of Kragujevac, Cara Dusana 34, 32000 Cacak, Republic of Serbia (Serbia); Maricic, A. [Joint Laboratory for Advanced Materials of the Serbian Academy of Science and Arts, Section for Amorphous Systems, Svetog Save 65, 32000 Cacak, Republic of Serbia (Serbia); Ribic Zelenovic, L. [Joint Laboratory for Advanced Materials of the Serbian Academy of Science and Arts, Section for Amorphous Systems, Svetog Save 65, 32000 Cacak, Republic of Serbia (Serbia); Faculty of Agronomy Cacak, University of Kragujevac, Cara Dusana 34, 32000 Cacak, Republic of Serbia (Serbia); Krstajic, N.; Spasojevic, P. [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Republic of Serbia (Serbia)

    2013-02-25

    Highlights: Black-Right-Pointing-Pointer Nanostructured Ni{sub 79.1}Co{sub 18.6}Cu{sub 2.3} powder was obtained by electrochemical deposition. Black-Right-Pointing-Pointer Correlation observed between electrical conductivity and absorbed hydrogen amount. Black-Right-Pointing-Pointer Hydrogen absorption/desorption mechanism was determined. - Abstract: Ni{sub 79.1}Co{sub 18.6}Cu{sub 2.3} powder was obtained by electrochemical deposition from an ammonium sulfate bath. The structure and surface morphology of the powder were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemically obtained Ni{sub 79.1}Co{sub 18.6}Cu{sub 2.3} alloy contained an amorphous phase and nanocrystals with an average size of 6.8 nm of FCC phase of the solid solution of cobalt and copper in nickel. Nanocrystals were characterized by a high average microstrain value and high minimum density of chaotically distributed dislocations. X-ray analysis also showed that powder hydrogenation at an elevated temperature of up to 200 Degree-Sign C did not change unit cell parameters and mean crystallite size value. SEM images show the formation of two shapes of powder particles: large cauliflower-like particles and small dendritic ones. Powder pressing at 10 MPa and at 25 Degree-Sign C gave samples that were analyzed for hydrogen absorption/desorption within the temperature range of 160-200 Degree-Sign C. Changes in electrical resistivity during absorption/desorption were monitored. The reciprocal value of resistivity (electrical conductivity) was found to increase linearly with increasing amount of absorbed hydrogen. The experimental results were used to propose an absorption/desorption mechanism. The adsorbed hydrogen molecule dissociates on alloy surface, forming adsorbed atoms. Adatoms penetrate and diffuse into the bulk of the alloy, simultaneously donating their electrons to the conduction band of the alloy. The increase in the concentration of free

  10. Experimental and theoretical investigation of Fe-catalysis phenomenon in hydrogen thermal desorption form hydrocarbon plasma-discharge films from T-10 tokamak

    Stankevich, V.G.; Svechnikov, N.Y.; Lebedev, A.M.; Menshikov, K.A.; Kolbasov, B.N.; Sukhanov, L.P.

    2017-01-01

    A comprehensive study of hydrocarbon films obtained in the plasma discharge of large fusion facilities will allow the minimization of parasitic capture. The investigation of the effect of Fe impurities on D 2 thermal desorption (TD) from homogeneous CD x films (x ∼ 0.5) formed in the D-plasma discharge of the T-10 tokamak were carried out. The experimental TD spectra of the films showed 2 groups of peaks at 650-850 K and 900-1000 K for 2 adsorption states. The main result of the iron catalysis effect consists in the shift of the high-temperature peak by -24 K and in the increase in the fraction of the weakly bonded adsorption states. To describe the effect of iron impurities on TD of hydrogen isotopes, a structural cluster model based on the interaction of the Fe + ion with the 1,3-C 6 H 8 molecule was proposed. The potential energy surfaces of chemical reactions with the H 2 elimination were calculated using ab initio methods of quantum chemistry. It was established that the activation barrier of hydrogen TD is reduced by about 1 eV due to the interaction of the Fe + ion with the π-subsystem of the 1,3-C 6 H 8 molecule leading to a redistribution of the double bonds along the carbon system

  11. Experimental and theoretical investigation of Fe-catalysis phenomenon in hydrogen thermal desorption from hydrocarbon plasma-discharge films from T-10 tokama

    Stankevich, Vladimir G.; Sukhanov, Leonid P.; Svechnikov, Nicolay Yu.; Lebedev, Alexey M.; Menshikov, Kostantin A.; Kolbasov, Boris N.

    2017-10-01

    Investigations of the effect of Fe impurities on D2 thermal desorption (TD) from homogeneous CDx films (x ˜ 0.5) formed in the D-plasma discharge of the T-10 tokamak were carried out. The experimental TD spectra of the films showed two groups of peaks at 650-850 K and 900-1000 K for two adsorption states. The main result of the iron catalysis effect consists in the shift of the high-temperature peak by -24 K and in the increase in the fraction of the weakly bonded adsorption states. To describe the effect of iron impurities on TD of hydrogen isotopes, a structural cluster model based on the interaction of the Fe+ ion with the 1,3-C6H8 molecule was proposed. The potential energy surfaces of chemical reactions with the H2 elimination were calculated using ab initio methods of quantum chemistry. It was established that the activation barrier of hydrogen TD is reduced by about 1 eV due to the interaction of the Fe+ ion with the π-subsystem of the 1,3-C6H8 molecule leading to a redistribution of the double bonds along the carbon system. Contribution to the topical issue "Plasma Sources and Plasma Processes (PSPP)"", edited by Luis Lemos Alves, Thierry Belmonte and Tiberiu Minea

  12. Analysis of the technique Thermal Desorption Spectroscopy (TDS) and its Application for the Characterization of Metal -Hydrogen Systems; Analisis de la Tecnica Espectroscopia de Desorcion Termica (TDS) y su Applicacion para la Caracterizacion de Sistemas Metal-Hydrogeno

    Castro, F J [Comision Nacional de Energia Atomica, Centro Atomico Bariloche (Argentina)

    2000-07-01

    We present the theoretical and experimental developments made to study the desorption of hydrogen from metallic samples by Thermal Desorption Spectroscopy (TDS). With this technique gas desorption is stimulated by the programmed heating of the sample. To perform the study we set up a newly designed equipment and develop theoretical models of the kinetic processes involved. The equipment and the models are used to analyze the desorption process in a real system. We begin by analyzing the models developed to interpret the results of the experiments. These models considersimultaneously bulk diffusion and surface reaction processes in metal-hydrogen systems with one or two thermodynamic phases. We present numerical results, computer simulations and analytical approximations of the original models. Based on these results we analyze the main features of the spectra for the different relevant kinetic processes, and determine the changes induced in them when material parameters (activation energies, geometry) or experimental parameters (heating speed, initial concentration) are modified.We present the original equipment, designed and constructed during this work to perform the TDS experiments. We describe its main characteristics, its components, its range of operation and its sensibility. We also offer an analysis of the background spectrum. We use the Pd-H system to test the equipment and the models. The samples chosen, powders, granules, foils and wires, were previously characterized to analyze their composition, their morphology and their characteristic size. We show the results of Scanning Electron Microscopy (SEM) observation, X ray diffraction (XRD) and Auger Electron Spectroscopy (AES) analysis.We then present and analyze in depth the experimental desorption spectra of the palladium powder. Based on the analysis we determine the rate limiting step for desorption and the characteristic activation energies. When the system is on the b phase (hydride) the rate

  13. Concerted Use of Slab and Cluster Models in an ab initio Study of Hydrogen Desorption from the Si(100) Surface

    Steckel, J. A.; Phung, T.; Jordan, K. D.; Nachtigall, Petr

    2001-01-01

    Roč. 105, č. 18 (2001), s. 4031-4038 ISSN 1089-5647 Institutional research plan: CEZ:AV0Z4040901 Keywords : silicon * surface * hydrogen Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.379, year: 2001

  14. Thermoanalytical investigation of the hydrogen absorption behaviour of Sm{sub 2}Fe{sub 17-x}Ga{sub x} at high hydrogen pressures

    Handstein, A.; Kubis, M.; Gebel, B.; Mueller, K.-H.; Schultz, L. [Institut fuer Festkoerper- und Werkstofforschung Dresden e.V. (Germany). Inst. fuer Metallische Werkstoffe; Gutfleisch, O.; Harris, I.R. [Institut fuer Festkoerper- und Werkstofforschung Dresden e.V. (Germany). Inst. fuer Metallische Werkstoffe]|[Birmingham Univ. (United Kingdom). School of Metallurgy and Materials

    1998-07-01

    The complete disproportionation of Sm{sub 2}Fe{sub 17-x}Ga{sub x} during annealing in hydrogen is hindered due to an increased stability of the compounds with a higher Ga content (x {>=} 1). Therefore the HD process as the first step of HDDR (hydrogenation-disproportionation-desorption-recombination) has to be carried out at a high hydrogen pressure for x {>=} 1. The hydrogen absorption behaviour of Sm{sub 2}Fe{sub 17-x}Ga{sub x} (x = 0, 0.5, 1 and 2) was investigated by means of hydrogen differential thermal analysis (HDTA) and high pressure differential scanning calorimetry (HPDSC) at hydrogen pressures up to 70 bar. A dependency of hydrogenation and disproportionation temperatures on hydrogen pressure and Ga content was found. The comparison with other substituents (M = Al and Si) instead of M = Ga showed an increased stability of Sm{sub 2}Fe{sub 17-x}M{sub x} compounds against disproportionation by hydrogen in the sequence Al, Ga and Si. The Curie temperatures of the interstitially hydrogenated Th{sub 2}Zn{sub 17}-type materials increase with the hydrogen pressure. In order to produce coercive and thermally stable Sm{sub 2}Fe{sub 15}Ga{sub 2}C{sub y} powder by means of the HDDR process, we recombined material disproportionated at different hydrogen pressures. Preliminary results of magnetic properties of this HDDR treated and gas-carburized Sm{sub 2}Fe{sub 15}Ga{sub 2}C{sub y} are discussed. (orig.)

  15. Ge(001):B gas-source molecular beam epitaxy: B surface segregation, hydrogen desorption, and film growth kinetics

    Kim, H.; Greene, J.E. [Materials Science Department, the Coordinated Science Laboratory and the Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States)

    1999-03-01

    Ultrahigh B-doped Ge(001) layers, with concentrations C{sub B} up to 8{times}10{sup 21} cm{sup {minus}3}, were grown by gas-source molecular beam epitaxy from Ge{sub 2}H{sub 6} and B{sub 2}H{sub 6} at temperatures T{sub s}=325{degree}C (in the surface-reaction-limited regime) and 600{degree}C (in the flux-limited regime). The samples were quenched, D site exchanged for H, and D{sub 2} temperature-programed desorption (TPD) used to determine B coverages {theta}{sub B} as a function of C{sub B} and T{sub s} by comparison with B-adsorbed Ge(001) reference samples with known {theta}{sub B} values. During Ge(001):B film growth, strong surface B segregation to the second layer was observed with surface-to-bulk B concentration ratios ranging up to 6000. The TPD spectra exhibited {alpha}{sub 2} and {alpha}{sub 1} peaks associated with dideuteride and monodeuteride desorption as well as lower-temperature B-induced {alpha}{sub 2}{sup {asterisk}} and {alpha}{sub 1}{sup {asterisk}} peaks associated with deuterium desorption from Ge{sup {asterisk}} surface atoms with B backbonds. Increasing {theta}{sub B} expanded the area under {alpha}{sub 2}{sup {asterisk}} and {alpha}{sub 1}{sup {asterisk}} at the expense of {alpha}{sub 2} and {alpha}{sub 1} and decreased the total D coverage {theta}{sub D}. The TPD results were used to determine the B segregation enthalpy, {minus}0.64 eV, and to explain and model the effects of high B coverages on Ge(001) growth kinetics. At T{sub s}=325{degree}C, where B segregation is kinetically hindered, film deposition rates R{sub Ge} are not a strong function of C{sub B}, exhibiting only a small decrease at C{sub B}{approx_gt}5{times}10{sup 18} cm{sup {minus}3}. However, at T{sub s}=600{degree}C, R{sub Ge} decreases by up to 40{percent} with increasing C{sub B}{approx_gt}1{times}10{sup 18} cm{sup {minus}3}. This is due primarily to the combination of B-induced Ge dimer vacancies and the deactivation of surface dangling bonds caused by charge transfer

  16. Indirect Medical Education and Disproportionate Share Adj...

    U.S. Department of Health & Human Services — Indirect Medical Education and Disproportionate Share Adjustments to Medicare Inpatient Payment Rates The indirect medical education (IME) and disproportionate share...

  17. Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen Storage Composite.

    Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

    2017-09-20

    The lightweight compound material NaNH 2 -NaBH 4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH 2 -NaBH 4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H 2 , NH 3 , B 2 H 6 , and N 2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B 6 H 12 also exists. The TG/DTA analyses show that the composite NaNH 2 -NaBH 4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na 3 (NH 2 ) 2 BH 4 hydride decomposes into Na 3 BN 2 and H 2 (200-350 °C); (2) remaining Na 3 (NH 2 ) 2 BH 4 reacts with NaBH 4 and Na 3 BN 2 , generating Na, BN, NH 3 , N 2 , and H 2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

  18. A new ternary magnesium-titanium hydride Mg{sub 7}TiH{sub x} with hydrogen desorption properties better than both binary magnesium and titanium hydrides

    Kyoi, Daisuke; Sato, Toyoto; Roennebro, Ewa; Kitamura, Naoyuki; Ueda, Atsushi; Ito, Mikio; Katsuyama, Shigeru; Hara, Shigeta; Noreus, Dag; Sakai, Tetsuo

    2004-06-09

    A magnesium based titanium doped hydride was prepared in a high-pressure anvil cell by reacting a mixture of MgH{sub 2} and TiH{sub 1.9} at 8 GPa and 873 K. The metal structure has a Ca{sub 7}Ge type structure (a=9.532(2) A, space group Fm3-barm (no. 225), Z=4, V=866.06 A{sup 3}). The refined metal atom composition Mg{sub 7}Ti was almost in line with EDS analysis. This means that the new magnesium-titanium hydride has a structure that is more related to TiH{sub 1.9} than to MgH{sub 2}. The thermal properties of the new compound were also studied by TPD analysis. The new hydride, Mg{sub 7}TiH{sub x} exhibits 5.5 mass% (x{approx}12.7) and decomposes into Mg and TiH{sub 1.9} upon releasing 4.7 mass% of hydrogen around 605 K, that is at a 130 and 220 K lower desorption temperature compared to MgH{sub 2} and TiH{sub 1.9}, respectively.

  19. Electrocatalytic activity of a mononuclear yttrium(III)–methyl orange complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles for adsorption/desorption of hydrogen

    Shafaie, Fahimeh [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Hadadzadeh, Hassan, E-mail: hadad@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Behnamfar, Mohammad Taghi [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan, 81746-73441 (Iran, Islamic Republic of)

    2016-12-01

    A new mononuclear yttrium(III) complex, [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}] (where MO{sup –} is methyl orange anion (4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate)), was synthesized in an aqueous solution. The complex was characterized by elemental analysis, UV/Vis, FT-IR, and single-crystal X-ray crystallography. The yttrium oxysulfate nanoparticles (Y{sub 2}O{sub 2}SO{sub 4}) were then prepared by calcination of [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}]. The obtained nanoparticles were characterized by FT-IR, X-ray diffraction analysis (XRD), and field-emission scanning electron microscopy (FE-SEM). The hydrogen adsorption/desorption (H{sub ads}/H{sub des}) behavior of the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles was studied at a carbon paste electrode (CPE) in H{sub 2}SO{sub 4} by cyclic voltammetry (CV). The recorded voltammograms exhibited a pair of peaks corresponding to the adsorption/desorption of hydrogen for the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. The results show a reversible hydrogen adsorption/desorption reaction for both compounds. The voltammograms of the nanoparticles indicate an excellent cycling stability for the adsorption/desorption of hydrogen. In addition, the linear sweep voltammetry (LSV) technique was used to investigate the electrocatalytic activity of both compounds for the hydrogen adsorption reaction. The linear voltammograms of both compounds demonstrate the excellent electrocatalytic activity for the hydrogen adsorption reaction. - Highlights: • Preparation of a new Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. • Investigation of the H{sub ads}/H{sub des} reaction for both compounds by voltammetry. • Observation of two peaks corresponding to the H{sub ads}/H{sub des} in both compounds. • An excellent cycling stability for the nanoparticles in H{sub 2}SO{sub 4}.

  20. Desorption process of hydrogen starting from the Mg{sub 2}NiH{sub 4} and Mg{sub 2}NiH{sub 0.3}; Proceso de desorcion de hidrogeno a partir del hidruro intermetalico Mg{sub 2}NiH{sub 4} y Mg{sub 2}NiH{sub 0.3}

    Iturbe G, J.L.; Basurto S, R.; Lopez M, B.E. [Departamento de Quimica, ININ, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    2002-07-01

    In this work the desorption velocity of H{sub 2} was determined starting from the magnesium nickel hydride once the reaction between the intermetallic and the hydrogen was realized, the compound were analysed by means of a thermogravimetric equipment, the conditions for carrying out the analysis were: 10 C by minute in nitrogen atmosphere at a volume of 50 ml by minute, subsequently the isotherms at different times were programmed and the desorption velocity of hydrogen was determined. The results show that the desorption velocity of hydrogen depends of the temperature, using only the nitrogen flux which acts as a carrier gas. Observing that the hydrogen liberation is carried out by means of two mechanisms according to the isotherms obtained. (Author)

  1. Data compilation for particle-impact desorption, 2

    Oshiyama, Takashi; Nagai, Siro; Ozawa, Kunio; Takeutchi, Fujio.

    1985-07-01

    The particle impact desorption is one of the elementary processes of hydrogen recycling in controlled thermonuclear fusion reactors. We have surveyed the literature concerning the ion impact desorption and photon stimulated desorption published through the end of 1984 and compiled the data on the desorption cross sections and yields with the aid of a computer. This report presents the results of the compilation in graphs and tables as functions of incident energy, surface temperature and surface coverage. (author)

  2. Salt disproportionation: A material science perspective.

    Thakral, Naveen K; Kelly, Ron C

    2017-03-30

    While screening the counter-ions for salt selection for an active pharmaceutical substance, there is often an uncertainty about disproportionation of the salt and hence physical stability of the final product formulation to provide adequate shelf life. Several examples of disproportionation reactions are reviewed to explain the concepts of pHmax, microenvironmental pH, and buffering capacity of excipients and APIs to gain mechanistic understanding of disproportionation reaction. Miscellaneous factors responsible for disproportionation are examined. In addition to the dissolution failure due to the formation of less soluble unionized form, various implications of the disproportionation are evaluated with specific examples. During lead optimization and early stages of development, when only a limited amount of material is available, use of predictive tools like mathematical models and model free kinetics to rank order the various counter-ions are discussed in detail. Finally, analytical methods and mitigation strategies are discussed to prevent the disproportionation by detecting it during early stages of drug development. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Disproportionate Poverty, Conservatism, and the Disproportionate Identification of Minority Students with Emotional and Behavioral Disorders

    Wiley, Andrew L.; Brigham, Frederick J.; Kauffman, James M.; Bogan, Jane E.

    2013-01-01

    Previous investigations of disproportionate representation of students from certain ethnic groups in special education have suggested that disproportionality is the result of bias against the members of overrepresented groups or, conversely, the result of disproportionate exposure to poverty for these students. Strong evidence in favor of either…

  4. Minorities Are Disproportionately Underrepresented in Special Education

    Morgan, Paul L.; Farkas, George; Hillemeier, Marianne M.; Mattison, Richard; Maczuga, Steve; Li, Hui; Cook, Michael

    2015-01-01

    We investigated whether minority children attending U.S. elementary and middle schools are disproportionately represented in special education. We did so using hazard modeling of multiyear longitudinal data and extensive covariate adjustment for potential child-, family-, and state-level confounds. Minority children were consistently less likely…

  5. Stimulated desorption induced by hydrogen aggregates (E ≤120 keV/u) and by heavy ions (E ≤ 400 keV/u). Analytical applications

    Oladipo, A.

    1988-03-01

    This work presents an original group of results on stimulated desorption induced by H n + clusters (n up to 61) at 600 keV on insulating samples. This phenomenom has been applied to surface microanalysis using both these particles and MeV argon ions. A time of flight spectrometer is used for the secondary ion detection. As far as clusters are concerned and for CsI material it is shown that the Cs + yield varies quadratically with the stopping power for these cluster, both above and below the BOHR velocity, v 0 . Such a trend is based on a coherent interpretation of the role of collective and individual interactions leading to the energy deposit. The study of H + variation is not only in agreement with this interpretation but also gives some new informations on the interaction below v 0 . As for the organic material, phenylalanine, we show the qualitative applicability of the model of intact molecule desorption from the periphery of the primary particle track. The high values of the measured ion yields (up to 100%), allows the use of low intensity ion beams using collimators of 2 μm diameter. The optimum lateral resolution has not been obtained with clusters due to technical limitations, but with the Ar ion irradiation system; a value of 10 μm has been obtained. On the other hand, marked differences have been observed between various alkali compounds, for which we make a tentative interpretation. Finally the evolution of desorption yields with the particle fluence constitutes an insight into the role played by the energy density on material modification under irradiation [fr

  6. Symproportionation versus Disproportionation in Bromine Redox Systems

    Toporek, Marcin; Michałowska-Kaczmarczyk, Anna M.; Michałowski, Tadeusz

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • The disproportionation and symproportionation of bromine in different media is presented. • All the redox systems are elaborated according to the principles of the generalized approach to electrolytic redox systems (GATES/GEB). • All physicochemical knowledge is involved in the algorithm applied for this purpose. • The graphical representation of the systems is the basis of gaining the detailed physicochemical knowledge on the systems in question. -- Abstract: The paper refers to dynamic (titration) redox systems where symproportionation or disproportionation of bromine species occur. The related systems are modeled according to principles assumed in the Generalized Approach to Electrolytic Redox Systems (GATES), with Generalized Electron Balance (GEB) concept involved in the GATES/GEB software. The results obtained from calculations made with use of iterative computer programs prepared according to MATLAB computational software, are presented graphically, as 2D and 3D graphs

  7. [Liability in Anaesthesiology: theory of disproportionate damage].

    Galán Gutiérrez, J C; Galán Cortés, J C

    2013-10-01

    An analysis is made of the controversial application of the theory of disproportionate damage in the anaesthetic act, due to the high inherent risk, and regardless of the seriousness and importance of the surgery being performed. The existence of a disproportionate damage, that is, damage not foreseen nor accountable within the framework of the professional performance of the anaesthetist, does not by itself determine the existence of liability on the part of the anaesthetist, but the demand from the professionals themselves for a coherent explanation of the serious disagreement between the initial risk implied by their actions and the final consequence produced. Copyright © 2012 Sociedad Española de Anestesiología, Reanimación y Terapéutica del Dolor. Published by Elsevier España. All rights reserved.

  8. Stability of the hydrogen absorption and desorption plateaux in LaNi[sub 5]-H. Pt. 3. Experimental observations of compositional inhomogeneities due to temperature gradients

    Kisi, E H [Newcastle upon Tyne Univ. (United Kingdom). Dept. of Mechanical Engineering; Gray, E MacA [School of Science, Griffith University, Brisbane, Qld. 4111 (Australia)

    1995-01-15

    It has been predicted by Pons and Dantzer that temperature gradients due to the released enthalpy of H absorption-desorption will generate macroscopic inhomogeneities of the [alpha]/[beta] phase proportions in metal hydrides. We used in situ X-ray diffraction and in situ neutron diffraction respectively to study the growth of [beta]-LaNi[sub 5]-H at the free surface, and [beta]-LaNi[sub 5]-D in the bulk of powdered samples. It was found that a macroscopic compositional inhomogeneity does occur, and can be so severe that the free surface of the sample remains pure [alpha] phase while the bulk of the sample is rich in [beta] phase. ((orig.))

  9. Hydrogen absorption/desorption characteristics of room temperature ZrMn2-xNix system (x = 1.25-1.50)

    Kumar, Vinod; Pukazhselvan, D.; Singh, S.K.; Tyagi, A.K.

    2014-01-01

    The present communication deals with the hydrogen storage characteristics of C15 laves phase ZrMn 2-x Ni x system tailored within the x values of 1.25 to 1.50. Drastic variations in thermodynamics of the hydride phase is observed for any little changes of concentration x within this narrow range. The most promising room temperature hydrogen storage materials are found to be formed within the range of 1.35 to 1.45 where ∼ 2.5 to 2.9 H/F.U. can be reversibly stored under the ideal operating conditions. The heat of the reaction is found to be ∼ 17 kJ/mol, which means these are promising candidates for stationary and short range mobile applications. The phase structural features and the thermodynamic aspects of all the materials are discussed in detail. (author)

  10. Hydrogen retention studies on lithiated tungsten exposed to glow discharge plasmas under varying lithiation environments using Thermal Desorption Spectroscopy and mass spectrometry

    Castro, A. de, E-mail: alfonso.decastro@ciemat.es [Fusion National Laboratory-CIEMAT, Av Complutense 40, 28040 Madrid (Spain); Valson, P. [Max-Planck-Institut für Plasmaphysik, Wendelsteinstraße 1, 17491 Greifswald (Germany); Tabarés, F.L. [Fusion National Laboratory-CIEMAT, Av Complutense 40, 28040 Madrid (Spain)

    2017-04-15

    For the design of a Fusion Reactor based on a liquid lithium divertor target and a tungsten first wall at high temperature, the interaction of the wall material with plasmas of significant lithium content must be assessed, as issues like fuel retention, tungsten embrittlement and enhanced sputtering may represent a showstopper for the selection of the first wall material compatible with the presence of liquid metal divertor. In this work we address this topic for the first time at the laboratory level, hot W samples (100 °C) have been exposed to Glow Discharges of H{sub 2} or Li-seeded H{sub 2} followed by in situ thermal desorption studies (TDS) of the uptake of H{sub 2} on the samples. Pure and pre-lithiated tungsten was investigated in order to evaluate the differential effect of Li ion implantation on H retention. Global particle balance was also used for the determination of trapped H into the full W wall of the plasma chamber. A factor of 3-4 lower retention was deduced for samples and main W wall exposed to H/Li plasma than that measured on pre-lithiated W.

  11. Interrelation between hydrogen desorption kinetics and structure of (Mg.sub.2./sub.Ni)H.sub.x./sub. and hydrogenated eutectic (Mg/Mg.sub.2./sub.Ni)H.sub.y./sub

    Čermák, Jiří; Král, Lubomír

    289-292, - (2009), s. 167-174 ISSN 1012-0386. [DIMAT 2008, International Conference on Diffusion in Materials /7./. Lanzarote, Canary Islands, 28.10.2008-31.10.2008] R&D Projects: GA ČR GA106/07/0010 Institutional research plan: CEZ:AV0Z20410507 Keywords : magnesium alloys * hydrogen diffusion * hydrogen- storage materials Subject RIV: BJ - Thermodynamics http://www.scientific.net/DDF.289-292.167/

  12. Hydrogen.

    Bockris, John O'M

    2011-11-30

    The idea of a "Hydrogen Economy" is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO₂ in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H₂ from the electrolyzer. Methanol made with CO₂ from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  13. Activated aluminum hydride hydrogen storage compositions and uses thereof

    Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

    2010-11-23

    In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

  14. Hydrogen

    John O’M. Bockris

    2011-11-01

    Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  15. Site Specificity in Femtosecond Laser Desorption of Neutral H Atoms from Graphite(0001)

    Frigge, R.; Hoger, T.; Siemer, B.

    2010-01-01

    Femtosecond laser excitation and density functional theory reveal site and vibrational state specificity in neutral atomic hydrogen desorption from graphite induced by multiple electronic transitions. Multimodal velocity distributions witness the participation of ortho and para pair states...... of chemisorbed hydrogen in the desorption process. Very slow velocities of 700 and 400  ms-1 for H and D atoms are associated with the desorption out of the highest vibrational state of a barrierless potential....

  16. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  17. Ascorbyl radical disproportionation in reverse micellar systems

    Gębicki, J. L.; Szymańska-Owczarek, M.; Pacholczyk-Sienicka, B.; Jankowski, S.

    2018-04-01

    Ascorbyl radical was generated by the pulse radiolysis method and observed with the fast kinetic spectrophotometry within reverse micelles stabilized by AOT in n-heptane or by Igepal CO-520 in cyclohexane at different water to surfactant molar ratio, w0. Rate constants for the disproportionation of the ascorbyl radicals were smaller than those for intermicellar exchange for both type of reverse micelles and slower than those in homogeneous aqueous solutions. However, they increased with increasing w0 for AOT/n-heptane system, while they decreased for Igepal CO-520 system. The absorption spectra of ascorbic acid AOT/n-heptane reverse micellar system showed that the "pH" sensed by this molecule is lower than that in respective homogeneous aqueous solutions. The obtained results were rationalized taking into account three main factors (i) preferential location of ascorbic acid molecules in the interfacial region of the both types of reverse micelles; (ii) postulate that the pH of the interface is lower than that of the water pool of reverse micelles and (iii) different structure of the interface of the reverse micelles made by AOT in n-heptane and those formed by Igepal CO-520 I cyclohexane. Some possible consequences of these findings are discussed.

  18. Deuterium desorption from tungsten using laser heating

    J.H. Yu

    2017-08-01

    Full Text Available Retention and desorption of hydrogenic species need to be accurately modeled to predict the tritium inventory of next generation fusion devices, which is needed both for tritium fuel recovery and for tritium safety concerns. In this paper, experiments on thermal desorption of deuterium from intrinsic polycrystalline tungsten defects using laser heating are compared to TMAP-7 modeling. The samples during deuterium plasma exposure were at a temperature of 373K for this benchmark study with ion fluence of 0.7–1.0 ×1024Dm−2. Following plasma exposure, a fiber laser (λ= 1100nm heated the samples to peak surface temperatures ranging from ∼500 to 1400K with pulse widths from 10ms to 1s, and 1 to 10 pulses applied to each sample. The remaining deuterium retention was measured using temperature programmed desorption (TPD. Results show that > 95% of deuterium is desorbed when the peak surface temperature reached ∼950K for > 1s. TMAP-7 is used to predict deuterium desorption from tungsten for a range of surface temperatures and heating durations, and is compared to previous work on desorption from beryllium codeposits.

  19. An infrared measurement of chemical desorption from interstellar ice analogues

    Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

    2018-03-01

    In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

  20. Testosterone sorption and desorption: Effects of soil particle size

    Qi, Yong, E-mail: yqi01@unomaha.edu [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Zhang, Tian C. [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Ren, Yongzheng [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2014-08-30

    Graphical abstract: - Highlights: • Smaller soil particles have higher sorption and lower desorption rates. • The sorption capacity ranks as clay > silt > sand. • Small particles like clays have less potential for desorption. • Colloids (clays) have high potential to facilitate the transport of hormones in soil–water environments. - Abstract: Soils contain a wide range of particles of different diameters with different mobility during rainfall events. Effects of soil particles on sorption and desorption behaviors of steroid hormones have not been investigated. In this study, wet sieve washing and repeated sedimentation methods were used to fractionate the soils into five ranges. The sorption and desorption properties and related mechanisms of testosterone in batch reactors filled with fractionated soil particles were evaluated. Results of sorption and desorption kinetics indicate that small soil particles have higher sorption and lower desorption rates than that of big ones. Thermodynamic results show the sorption processes are spontaneous and exothermal. The sorption capacity ranks as clay > silt > sand, depending mainly on specific surface area and surface functional groups. The urea control test shows that hydrogen bonding contributes to testosterone sorption onto clay and silt but not on sand. Desorption tests indicate sorption is 36–65% irreversible from clay to sand. Clays have highest desorption hysteresis among these five soil fractions, indicating small particles like clays have less potential for desorption. The results provide indirect evidence on the colloid (clay)-facilitated transport of hormones (micro-pollutants) in soil environments.

  1. Thermal stability of hydrogenated small-diameter carbon nanotubes

    Podlivaev, A. I., E-mail: AIPodlivayev@mephi.ru; Openov, L. A. [National Research Nuclear University “MEPhI” (Russian Federation)

    2017-02-15

    The initial stage of hydrogen desorption from fully hydrogenated carbon nanotubes (3.0) and (2.2) is numerically studied by the molecular dynamics method. The temperature dependence of the desorption rate is directly determined at T = 1800–2500 K. The characteristic desorption times are determined at temperatures outside this range by extrapolation. It is shown that hydrogen desorption leads to the appearance of electronic states in the band gap.

  2. Effect Of The Desorption-Recombination Temperature On The Microstructure And Magnetic Properties Of HDDR Processed Nd-Fe-B Powders

    Lee J.-G.

    2015-06-01

    Full Text Available The effect of the desorption-recombination temperature on the microstructure and magnetic properties of hydrogenation-disproportionation-desorption-recombination (HDDR processed Nd-Fe-B powders was studied. The NdxB6.4Ga0.3Nb0.2Febal (x=12.5-13.5, at.% casting alloys were pulverized after homogenizing annealing, and then subjected to HDDR treatment. During the HDDR process, desorption-recombination (DR reaction was induced at two different temperature, 810°C and 820°C. The higher Nd content resulted in enhanced coercivity of the HDDR powder, and which was attributed to the thicker and more uniform Nd-rich phase along grain boundaries. But this uniform Nd-rich phase induced faster grain growth. The remanence of the powder DR-treated at 820°C is higher than that DR-treated at 810°C. In addition, it was also confirmed that higher DR temperature is much more effective to improve squareness.

  3. 42 CFR 412.320 - Disproportionate share adjustment factor.

    2010-10-01

    ... 42 Public Health 2 2010-10-01 2010-10-01 false Disproportionate share adjustment factor. 412.320... Capital-Related Costs § 412.320 Disproportionate share adjustment factor. (a) Criteria for classification... adjustment factor. (1) If a hospital meets the criteria in paragraph (a)(1) of this section for a...

  4. NO2 disproportionation for the IR characterisation of basic zeolites.

    Marie, Olivier; Malicki, Nicolas; Pommier, Catherine; Massiani, Pascale; Vos, Ann; Schoonheydt, Robert; Geerlings, Paul; Henriques, Carlos; Thibault-Starzyk, Fréderic

    2005-02-28

    NO2 disproportionation on alkaline zeolites is used to generate nitrosonium (NO+) and nitrate ions on the surface, and the infrared vibrations observed are very sensitive to the cation chemical hardness and to the basicity of zeolitic oxygen atoms.

  5. Hydrogen retention properties of lithium film

    Kanaya, Koh; Yamauchi, Yuji; Hirohata, Yuko; Hino, Tomoaki; Mori, Kintaro

    1998-01-01

    Hydrogen retention properties of Li films and lithium oxide-lithium hydroxide (Li 2 O-LiOH) mixed films were investigated by two methods, hydrogen ion irradiation and hydrogen glow discharge. In a case of the hydrogen ion irradiation, thermal desorption spectrum of hydrogen retained in Li 2 O-LiOH film had two desorption peaks at around 470 K and 570 K. The ratio between retained hydrogen and Li atom was about 0.7. In a case of the hydrogen glow discharge, the hydrogen was also gettered in Li film during the discharge. The ratio of H/Li was almost 0.9. Most of gettered hydrogen desorbed by a baking with a temperature of 370 K. On the contrary, when the Li film exposed to the atmosphere was irradiated by the hydrogen plasma, the desorption of H 2 O was observed in addition to the adsorption of H 2 . (author)

  6. Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

    Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

    2013-11-01

    Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

  7. Cyclic hydrogenation stability of γ-hydrides for Ti{sub 25}V{sub 35}Cr{sub 40} alloys doped with carbon

    Shen, Chia-Chieh, E-mail: ccshen@saturn.yzu.edu.tw [Department of Mechanical Engineering, Yuan Ze University, Chungli 32003, Taiwan (China); Graduate School of Renewable Energy and Engineering, Yuan Ze University, Chungli 32003, Taiwan (China); Fuel Cell Center, Yuan Ze University, Chungli 32003, Taiwan (China); Li, Hsueh-Chih [Graduate School of Renewable Energy and Engineering, Yuan Ze University, Chungli 32003, Taiwan (China)

    2015-11-05

    An automatic Sievert's apparatus equipped with a temperature-programmed desorption spectrometer was constructed to study the stability of annealed Ti{sub 25}V{sub 35}Cr{sub 40}C{sub x} (x = 0 and 0.1) alloy under cyclic hydrogenation at 6 N H{sub 2}. The specimens were tested at 30 °C with a hydrogen loading of around 1.00 H/M, which enabled the phase transformation from β-to γ-hydrides. After 500 cycles, 83% and 90% of the initial hydrogen capacities were preserved for Ti{sub 25}V{sub 35}Cr{sub 40} and Ti{sub 25}V{sub 35}Cr{sub 40}C{sub 0.1}, respectively. Therefore, a small amount of C doping was effective in reducing the hydrogenation degradation of Ti{sub 25}V{sub 35}Cr{sub 40}. The hydrogenation degradation of Ti{sub 25}V{sub 35}Cr{sub 40} was examined by measuring the P–C isotherms, temperature-programmed desorption spectra, and X-ray diffraction patterns. The degradation was ascribed to intrinsic disproportionation, i.e., Ti{sub 0.25}V{sub 0.35}Cr{sub 0.40} + 0.88H{sub 2} → yTiH{sub 2} + Ti{sub 0.25−y}V{sub 0.35}Cr{sub 0.40}H{sub 1.76–2y}, where the coefficient y indicates the amount of Ti-rich precipitate. The better cyclic hydrogenation stability of Ti{sub 25}V{sub 35}Cr{sub 40}C{sub 0.1} was related to the suppression of intrinsic disproportionation by the presence of carbon atoms in the body-centered-cubic lattice. - Highlights: • The stability of γ-hydride for Ti{sub 25}V{sub 35}Cr{sub 40} alloys was examined for 500 cycles. • The γ-hydride of Ti{sub 25}V{sub 35}Cr{sub 40} alloy degraded by intrinsic disproportionation. • The disproportionation of γ-hydride can be suppressed through carbon inclusion.

  8. New insights into the acid mediated disproportionation of pentavalent uranyl

    Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

    2010-07-01

    The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

  9. Elemental sulfur and thiosulfate disproportionation by Desulfocapsa sulfoexigens sp. nov., a new anaerobic bacterium isolated from marine surface sediment

    Finster, Kai; Liesack, Werner; Thamdrup, Bo

    1998-01-01

    A mesophilic, anaerobic, gram-negative bacterium, strain SB164P1, was enriched and isolated from oxidized marine surface sediment with elemental sulfur as the sole energy substrate in the presence of ferrihydrite. Elemental sulfur was disproportionated to hydrogen sulfide and sulfate. Growth was ...

  10. Elemental sulfur and thiosulfate disproportionation by Desulfocapsa sulfoexigens sp. nov., a new anaerobic bacterium isolated from marine surface sediment.

    Finster, K; Liesack, W; Thamdrup, B

    1998-01-01

    A mesophilic, anaerobic, gram-negative bacterium, strain SB164P1, was enriched and isolated from oxidized marine surface sediment with elemental sulfur as the sole energy substrate in the presence of ferrihydrite. Elemental sulfur was disproportionated to hydrogen sulfide and sulfate. Growth was observed exclusively in the presence of a hydrogen sulfide scavenger, e.g., ferrihydrite. In the absence of a scavenger, sulfide and sulfate production were observed but no growth occurred. Strain SB164P1 grew also by disproportionation of thiosulfate and sulfite. With thiosulfate, the growth efficiency was higher in ferrihydrite-supplemented media than in media without ferrihydrite. Growth coupled to sulfate reduction was not observed. However, a slight sulfide production occurred in cultures incubated with formate and sulfate. Strain SB164P1 is the first bacterium described that grows chemolithoautotrophically exclusively by the disproportionation of inorganic sulfur compounds. Comparative 16S rDNA sequencing analysis placed strain SB164P1 into the delta subclass of the class Proteobacteria. Its closest relative is Desulfocapsa thiozymogenes, and slightly more distantly related are Desulfofustis glycolicus and Desulforhopalus vacuolatus. This phylogenetic cluster of organisms, together with members of the genus Desulfobulbus, forms one of the main lines of descent within the delta subclass of the Proteobacteria. Due to the common phenotypic characteristics and the phylogenetic relatedness to Desulfocapsa thiozymogenes, we propose that strain SB164P1 be designated the type strain of Desulfocapsa sulfoexigens sp. nov.

  11. Catabolic thiosulfate disproportionation and carbon dioxide reduction in strain DCB-1, a reductively dechlorinating anaerobe

    Mohn, W.W.; Tiedje, J.M. (Michigan State Univ., East Lansing (USA))

    1990-04-01

    Strain DCB-1 is a strict anaerobe capable of reductive dehalogenation. We elucidated metabolic processes in DCB-1 which may be related to dehalogenation and which further characterize the organism physiologically. Sulfoxy anions and CO2 were used by DCB-1 as catabolic electron acceptors. With suitable electron donors, sulfate and thiosulfate were reduced to sulfide. Sulfate and thiosulfate supported growth with formate or hydrogen as the electron donor and thus are probably respiratory electron acceptors. Other electron donors supporting growth with sulfate were CO, lactate, pyruvate, butyrate, and 3-methoxybenzoate. Thiosulfate also supported growth without an additional electron donor, being disproportionated to sulfide and sulfate. In the absence of other electron acceptors, CO2 reduction to acetate plus cell material was coupled to pyruvate oxidation to acetate plus CO2. Pyruvate could not be fermented without an electron acceptor. Carbon monoxide dehydrogenase activity was found in whole cells, indicating that CO2 reduction probably occurred via the acetyl coenzyme A pathway. Autotrophic growth occurred on H2 plus thiosulfate or sulfate. Diazotrophic growth occurred, and whole cells had nitrogenase activity. On the basis of these physiological characteristics, DCB-1 is a thiosulfate-disproportionating bacterium unlike those previously described.

  12. Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

    Silver, G.L.

    2014-01-01

    Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

  13. Ultrafine hydrogen storage powders

    Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

    2000-06-13

    A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

  14. Mutual Effects of Hydrogenation and Deformation in Ti-Nb Alloys

    Zander, D

    2002-01-01

    ...), transmission electron microscopy (TEM), thermal desorption spectroscopy (TDS), and microhardness tests, the influence of hydrogen at high fugacities on the phase stability, desorption behavior, and microhardness in Ti-Nb (20 to 45 wt pct Nb...

  15. Hydrogen storage in carbon nanostruc

    Hirscher, M.; Becher, M.; Haluska, M.; Quintel, A.; Skakalova, V.; Choi, M.; Dettlaff-Weglikowska, U.; Roth, S.; Stepanek, I.; Bernier, P.; Leonhardt, A.; Fink, J.

    2002-01-01

    The paper gives a critical review of the literature on hydrogen storage in carbon nanostructures. Furthermore, the hydrogen storage of graphite, graphite nanofibers (GNFs), and single-walled carbon nanotubes (SWNTs) was measured by thermal desorption spectroscopy (TDS). The samples were ball milled

  16. Gas desorption properties of ammonia borane and metal hydride composites

    Matin, M.R.

    2009-01-01

    'Full text': Ammonia borane (NH 3 BH 3 ) has been of great interest owing to its ideal combination of low molecular weight and high H 2 storage capacity of 19.6 mass %, which exceeds the current capacity of gasoline. DOE's year 2015 targets involve gravimetric as well as volumetric energy densities. In this work, we have investigated thermal decomposition of ammonia borane and calcium hydride composites at different molar ratio. The samples were prepared by planetary ball milling under hydrogen gas atmosphere pressure of 1Mpa at room temperature for 2, and 10 hours. The gas desorption properties were examined by thermal desorption mass spectroscopy (TDMS). The identification of phases was carried out by X-ray diffraction. The results obtain were shown in fig (a),(b),and (c). Hydrogen desorption properties were observed at all molar ratios, but the desorption temperature is significantly lower at around 70 o C at molar ratio 1:1 as shown in fig (c), and unwanted gas (ammonia) emissions were remarkably suppressed by mixing with the calcium hydride. (author)

  17. Sorption and desorption of diuron in Oxisol under biochar application

    Fabiano André Petter

    Full Text Available ABSTRACT The objective of this study was to verify the kinetics of sorption and desorption of diuron in an Oxisol under application of biochar. The samples were collected in a field experiment conducted in randomized design blocks consisted of 2 base fertilization levels (0 and 400 kg∙ha−1 NPK 00-20-20 fertilizer formula and 3 doses of biochar (0, 8 and 16 Mg∙ha−1. In the evaluation of sorption and desorption, Batch Equilibrium method was used. The kinetics of sorption and desorption of diuron, total organic carbon, fulvic acid, humic acid and humin, pH and partition coefficient to organic carbon were evaluated. The Freundlich isotherm was adjusted appropriately to describe diuron sorption kinetics in all the studied treatments. The application of biochar provided increment in the sorption (Kf and reduction in the desorption of diuron in 64 and 44%, respectively. This effect is attributed to the biochar contribution to the total organic carbon and C-humin and of these to diuron through hydrophobic interactions and hydrogen bonds. The positive correlation between the partition coefficient to organic carbon and Kf confirms the importance of soil organic compartment in the sorption of diuron. There was no competition of NPK fertilizer for the same sorption site of diuron. The increase and reduction in sorption and desorption, respectively, show that the application of biochar is an important alternative for the remediation of soil leaching of diuron, especially in sandy soils.

  18. Are disproportionate costs of the WFD an issue?

    Jacobsen, Brian H.; Olsen, Søren Bøye; Jensen, Carsten Lynge

    water catchment areas in Denmark where costs and benefits are estimated for each of the areas. In order to support and validate the main findings from the 23 CBAs, a sensitivity analysis is conducted where costs and benefits are assessed in a less conservative way. The results in terms of net present...... value for each catchment from the conservative approach suggest as a preliminary indication that costs could be disproportionate in several Danish water catchment areas. The sensitivity analysis further helps to pinpoint two or three areas where we suggest that more detailed and precise CBAs are needed...

  19. Complex hydrides for hydrogen storage

    Zidan, Ragaiy

    2006-08-22

    A hydrogen storage material and process of forming the material is provided in which complex hydrides are combined under conditions of elevated temperatures and/or elevated temperature and pressure with a titanium metal such as titanium butoxide. The resulting fused product exhibits hydrogen desorption kinetics having a first hydrogen release point which occurs at normal atmospheres and at a temperature between 50.degree. C. and 90.degree. C.

  20. Desorption of H atoms from graphite (0001) using XUV free electron laser pulses

    Siemer, B.; Olsen, Thomas; Hoger, T.

    2010-01-01

    The desorption of neutral H atoms from graphite with femtosecond XUV pulses is reported. The velocity distribution of the atoms peaks at extremely low kinetic energies. A DFT-based electron scattering calculation traces this distribution to desorption out of specific adsorption sites on graphite......, and identifies the highest vibrational state in the adsorbate potential as a major source for the slow atoms. It is evident that multiple electron scattering processes are required for this desorption. A direct electronic excitation of a repulsive hydrogen-carbon bond seems not to be important....

  1. Effects of an electron beam on adsorption and desorption of ammonia on ruthenium (0001)

    Danielson, L.R.; Dresser, M.J.; Donaldson, E.E.; Sandstrom, D.R.

    1978-01-01

    The effects of an electron beam on ammonia adsorption and desorption on Ru(0001) have been investigated by Auger electron spectroscopy, low-energy electron diffraction, and thermal flash desorption. Appreciable adsorption at room temperature occurred only on the area of the Ru crystal which had been bombarded by an electron beam during dosing. The adsorption rate was a function of beam current density and ammonia pressure, and an apparent (2x2) diffraction pattern appeared in the area bombarded by the electron beam. Electron bombardment of the molecular γ states of ammonia followed by flash desorption showed that less ammonia and more hydrogen and nitrogen were desorbed as the bombardment time increased. An analysis of this process based on electron-induced dissociation of the ammonia molecule yielded an effective initial dissociation cross section of 3x10 -6 cm 2 . Hydrogen flash desorption spectra after bombardment of the γ states obeying first order kinetics with desorption energies of 0.78 and 1.0 eV. Electron bombardment of the γ states for short times produced the same effects on the ammonia flash desorption spectra as preadsorption of hydrogen. (Auth.)

  2. Absorption/desorption in sprays

    Naimpally, A.

    1987-01-01

    This survey paper shall seek to present the present state of knowledge concerning absorption and desorption in spray chambers. The first part of the paper presents the theories and formulas for the atomization and break-up of sprays in nozzles. Formulas for the average (sauter-mean) diameters are then presented. For the case of absorption processes, the formulas for the dimensionless mass transfer coefficients is in drops. The total; mass transfer is the total of the transfer in individual drops. For the case of desorption of sparingly soluble gases from liquids in a spray chamber, the mass transfer occurs in the spray just at the point of break-up of the jet. Formulas for the desorption of gases are presented

  3. The disproportionation of Pu4+ in nitric acid solutions

    Toth, L.M.; Bell, J.T.; Friedman, H.A.

    1990-01-01

    The Pu 4+ disproportionation equilibrium in nitric acid has been examined at ≤25deg C to extend our understanding and predictive ability with regard to species distribution under these conditions. Vis/UV absorption spectrophotometry has been used in a conventional manner to determine the concentrations of the various plutonium species. Values for the overall equilibrium quotient at 5, 15, and 25deg C were determined to be 0.098, 3.46, and 58.8, respectively, at zero ionic strength. From these values, the enthalpy of the reaction was found to be +52.7 kcal (220 kJ)/mol. The excellent reproducibility of the equilibrium quotients, even while parameters such as acid, nitrate ion and plutonium concentrations were changed, lend confidence to future predictive calculations regarding this reaction. (orig.)

  4. Gas desorption during friction of amorphous carbon films

    Rusanov, A; Fontaine, J; Martin, J-M; Mogne, T L; Nevshupa, R

    2008-01-01

    Gas desorption induced by friction of solids, i.e. tribodesorption, is one of the numerous physical and chemical phenomena, which arise during friction as result of thermal and structural activation of material in a friction zone. Tribodesorption of carbon oxides, hydrocarbons, and water vapours may lead to significant deterioration of ultra high vacuum conditions in modern technological equipment in electronic, optoelectronic industries. Therefore, knowledge of tribodesorption is crucial for the performance and lifetime of vacuum tribosystems. Diamond-like carbon (DLC) coatings are interesting materials for vacuum tribological systems due to their high wear resistance and low friction. Highly hydrogenated amorphous carbon (a-C:H) films are known to exhibit extremely low friction coefficient under high vacuum or inert environment, known as 'superlubricity' or 'superlow friction'. However, the superlow friction period is not always stable and then tends to spontaneous transition to high friction. It is supposed that hydrogen supply from the bulk to the surface is crucial for establishing and maintaining superlow friction. Thus, tribodesorption can serve also as a new technique to determine the role of gases in superlow friction mechanisms. Desorption of various a-C:H films, deposited by PECVD, ion-beam deposition and deposition using diode system, has been studied by means of ultra-high vacuum tribometer equipped with a mass spectrometer. It was found that in superlow friction period desorption rate was below the detection limit in the 0-85 mass range. However, transition from superlow friction to high friction was accompanied by desorption of various gases, mainly of H 2 and CH 4 . During friction transition, surfaces were heavily damaged. In experiments with DLC films with low hydrogen content tribodesorption was significant during the whole experiment, while low friction was not observed. From estimation of maximum surface temperature during sliding contact it

  5. In situ measurements of fuel retention by laser induced desorption spectroscopy in TEXTOR

    Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Stoschus, H.; Brezinsek, S.; Samm, U.; TEXTOR Team

    2011-12-01

    In future fusion devices such as ITER tritium retention due to tritium co-deposition in mixed material layers can be a serious safety problem. Laser induced desorption spectroscopy (LIDS) can measure the hydrogen content of hydrogenic carbon layers locally on plasma-facing components, while hydrogen is used as a tritium substitute. For several years, this method has been applied in the TEXTOR tokamak in situ during plasma operation to monitor the hydrogen content in space and time. This work shows the LIDS signal reproducibility and studies the effects of different plasma conditions, desorption distances from the plasma and different laser energies using a dedicated sample with constant hydrogen amount. Also the LIDS signal evaluation procedure is described in detail and the detection limits for different conditions in the TEXTOR tokamak are estimated.

  6. SPS Ion Induced Desorption Experiment

    Maximilien Brice

    2003-01-01

    This experiment will give a study about the induced desorption from heavy ion (Indium ion run from week 45 in SPS T4-H8 area) impacting LHC type graphite collimator. 4 different samples are located in the 4 chambers 90° one to each other: pure graphite, graphite with copper coating, graphite with NEG coating, 316LN stainless steal (reference).

  7. Carbon tetrachloride desorption from activated carbon

    Jonas, L.A.; Sansone, E.B.

    1981-01-01

    Carbon tetrachloride was desorbed from a granular activated carbon subsequent to its adsorption under various vapor exposure periods. The varied conditions of exposure resulted in a range of partially saturated carbon beds which, when followed by a constant flow rate for desorption, generated different forms of the desorbing concentration versus time curve. A method of analyzing the desorption curves is presented which permits extraction of the various desorbing rates from the different desorption and to relate this to the time required for such regeneration. The Wheeler desorption kinetic equation was used to calculate the pseudo first order desorption rate constant for the carbon. The desorption rate constant was found to increase monotonically with increasing saturation of the bed, permitting the calculation of the maximum desorption rate constant for the carbon at 100% saturation. The Retentivity Index of the carbon, defined as the dimensionless ratio of the adsorption to the desorption rate constant, was found to be 681

  8. Global forest loss disproportionately erodes biodiversity in intact landscapes.

    Betts, Matthew G; Wolf, Christopher; Ripple, William J; Phalan, Ben; Millers, Kimberley A; Duarte, Adam; Butchart, Stuart H M; Levi, Taal

    2017-07-27

    Global biodiversity loss is a critical environmental crisis, yet the lack of spatial data on biodiversity threats has hindered conservation strategies. Theory predicts that abrupt biodiversity declines are most likely to occur when habitat availability is reduced to very low levels in the landscape (10-30%). Alternatively, recent evidence indicates that biodiversity is best conserved by minimizing human intrusion into intact and relatively unfragmented landscapes. Here we use recently available forest loss data to test deforestation effects on International Union for Conservation of Nature Red List categories of extinction risk for 19,432 vertebrate species worldwide. As expected, deforestation substantially increased the odds of a species being listed as threatened, undergoing recent upgrading to a higher threat category and exhibiting declining populations. More importantly, we show that these risks were disproportionately high in relatively intact landscapes; even minimal deforestation has had severe consequences for vertebrate biodiversity. We found little support for the alternative hypothesis that forest loss is most detrimental in already fragmented landscapes. Spatial analysis revealed high-risk hot spots in Borneo, the central Amazon and the Congo Basin. In these regions, our model predicts that 121-219 species will become threatened under current rates of forest loss over the next 30 years. Given that only 17.9% of these high-risk areas are formally protected and only 8.9% have strict protection, new large-scale conservation efforts to protect intact forests are necessary to slow deforestation rates and to avert a new wave of global extinctions.

  9. Disproportionate Intrauterine Growth Intervention Trial At Term: DIGITAT

    Huisjes Anjoke JM

    2007-07-01

    Full Text Available Abstract Background Around 80% of intrauterine growth restricted (IUGR infants are born at term. They have an increase in perinatal mortality and morbidity including behavioral problems, minor developmental delay and spastic cerebral palsy. Management is controversial, in particular the decision whether to induce labour or await spontaneous delivery with strict fetal and maternal surveillance. We propose a randomised trial to compare effectiveness, costs and maternal quality of life for induction of labour versus expectant management in women with a suspected IUGR fetus at term. Methods/design The proposed trial is a multi-centre randomised study in pregnant women who are suspected on clinical grounds of having an IUGR child at a gestational age between 36+0 and 41+0 weeks. After informed consent women will be randomly allocated to either induction of labour or expectant management with maternal and fetal monitoring. Randomisation will be web-based. The primary outcome measure will be a composite neonatal morbidity and mortality. Secondary outcomes will be severe maternal morbidity, maternal quality of life and costs. Moreover, we aim to assess neurodevelopmental and neurobehavioral outcome at two years as assessed by a postal enquiry (Child Behavioral Check List-CBCL and Ages and Stages Questionnaire-ASQ. Analysis will be by intention to treat. Quality of life analysis and a preference study will also be performed in the same study population. Health technology assessment with an economic analysis is part of this so called Digitat trial (Disproportionate Intrauterine Growth Intervention Trial At Term. The study aims to include 325 patients per arm. Discussion This trial will provide evidence for which strategy is superior in terms of neonatal and maternal morbidity and mortality, costs and maternal quality of life aspects. This will be the first randomised trial for IUGR at term. Trial registration Dutch Trial Register and ISRCTN

  10. Design and construction of thermal desorption measurement system for tritium contained materials

    Hara, M.; Hatano, Y.; Calderoni, P.; Shimada, M.

    2014-01-01

    The dual-mode thermal desorption analysis system was designed and built in Idaho National Laboratory (INL) to examine the evolution of the hydrogen isotope gas from materials. The system is equipped with a mass spectrometer for stable hydrogen isotopes and an ionization chamber for tritium components. The performance of the system built was tested with using tritium contained materials. The evolution of tritiated gas species from contaminated materials was measured successfully by using the system. (author)

  11. Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO2(111)

    Sutton, Jonathan E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Overbury, Steven H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Beste, Ariana [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-03-24

    Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.

  12. ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

    ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

  13. Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111, Pt(100 e Pt(110 The correlation between the atomic surface structure and the reversible adsorption-desorption of hydrogen on single crystal Pt (111, Pt (100 and Pt (110 electrodes

    Valderi Pacheco dos Santos

    2001-12-01

    Full Text Available Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100, Pt(110 and Pt(111, in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

  14. English Writing Placement Recommendations at College of the Canyons: An Analysis of Disproportionate Impact.

    Gerda, Joseph

    A study was undertaken at California's College of the Canyons (CoC) to determine whether evidence existed of disproportionate impact in English course placement based on student ethnicity, gender, or age. Data were compiled for all 4,309 students tested between spring 1993 and fall 1995, while the standard for disproportionate impact was taken…

  15. English Reading Placement Recommendations at College of the Canyons: An Analysis of Disproportionate Impact.

    Gerda, Joseph

    A study was undertaken at California's College of the Canyons (CC) to determine whether evidence existed of disproportionate impact in English reading course placement based on student ethnicity, gender, or age. Data were compiled for all 4,312 students tested between spring 1993 and fall 1995, while the standard for disproportionate impact was…

  16. Hydrogen Sorption Performance of Pure Magnesium during Continued Cycling

    Vigeholm, B.; Kjøller, John; Larsen, B.

    1983-01-01

    Preliminary investigations of the hydrogen absorption - desorption by commercially pure magnesium powder under continuous operation show little or no reduction in hydrogen capacity up to 70 cycles and high temperature exposure exceeding 1200 h. Absorption was studied at 260°–425°C and hydrogen...

  17. Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles

    Griessen, R.P.; Strohfeldt, N.; Giessen, H.

    2015-01-01

    Palladium-hydrogen is a prototypical metal-hydrogen system. It is therefore not at all surprising that a lot of attention has been devoted to the absorption and desorption of hydrogen in nanosized palladium particles. Several seminal articles on the interaction of H with Pd nanocubes and

  18. High octane gasoline components from catalytic cracking gasoline, propylene, and isobutane by disproportionation, clevage and alkylation

    Banks, R.

    1980-07-08

    A process is described for producing high octane value gasoline which comprises in a disproportionation zone subjecting propylene and a mixture of propylene and ethylene obtained as hereinafter delineated to disproportionation conditions to produce a stream containing ethylene and a stream containing butenes, passing the ethylene-containing stream from said disproportionation zone together with a catalytic cracking gasoline to a cleavage zone under disproportionation conditions and subjecting the mixture of hydrocarbons therin to cleavage to produce said mixture of propylene and ethylene, a C/sub 5//sup +/ gasoline-containing product and butenes and wherein the butenes obtained in the overall operation of the disproportionation zone and the cleavage zone are passed to an alkylation zone wherein said butenes are used to alkylate an isoparaffin to produce additional high octane value product.

  19. Effect of oxygen on the hydrogenation properties of magnesium films

    Ostenfeld, Christopher Worsøe; Chorkendorff, Ib

    2006-01-01

    The effect of magnesium oxide on the magnesium and hydrogen desorption properties of magnesium films have been investigated. We find that by capping metallic magnesium films with oxide overlayers the apparent desorption energy of magnesium is increased from 146 kJ/mol to 314 kJ/mol. The results...... are discussed in light of previous investigations of ball-milled magnesium powders....

  20. New perspectives in vacuum high voltage insulation. II. Gas desorption

    Diamond, W T

    1998-01-01

    An examination has been made of gas desorption from unbaked electrodes of copper, niobium, aluminum, and titanium subjected to high voltage in vacuum. It has been shown that the gas is composed of water vapor, carbon monoxide, and carbon dioxide, the usual components of vacuum outgassing, plus an increased yield of hydrogen and light hydrocarbons. The gas desorption was driven by anode conditioning as the voltage was increased between the electrodes. The gas is often desorbed as microdischarges-pulses of a few to hundreds of microseconds-and less frequently in a more continuous manner without the obvious pulsed structure characteristic of microdischarge activity. The quantity of gas released was equivalent to many monolayers and consisted mostly of neutral molecules with an ionic component of a few percent. A very significant observation was that the gas desorption was more dependent on the total voltage between the electrodes than on the electric field. It was not triggered by field-emitted electrons but oft...

  1. Study of the influence of the temperature in the magnetic properties and in microstructure in the permanent magnets Pr-Fe-B-Nb-Co based obtained by hydrogen

    Silva, Suelanny Carvalho da

    2007-01-01

    Fine magnetic powders were produced using the hydrogenation disproportionation desorption and recombination (HDDR) process. The first stage in this work involved an investigation of the effect of the Co content and range of desorption/ recombination temperatures between 800 and 900 deg C with the purpose of optimizing the HDDR treatment for Pr 14 Fe 80 B 6 and Pr 14 Fe bal Co x B 6 Nb 0,1 (x= 0, 4, 8, 10, 12, 16) alloys. The cast alloys were annealed at 1100 deg C for 20 hours for homogenization. The processing temperature (desorption/ recombination) affected the microstructure and magnetic properties of the bonded magnets. The alloy with low cobalt content (4 at.%) required the highest reaction temperature (880 deg C) to yield anisotropic bonded magnets. The optimum temperature for alloys with 8 at.% Co and 10 at.% Co were 840 deg C and 820 deg C, respectively. Alloys with high cobalt content (12 at.% and 16 at.%) were processed at 840 deg C. The optimum desorption temperature for achieving high anisotropy for Pr 14 Fe 80 B 6 and Pr 14 Fe 79,9 B 6 Nb 0,1 was 820 deg C. The best remanence (862 mT) was achieved with the Pr 14 Fe 67,9 B 6 Co 12 Nb 0,1 magnet, processed at 840 deg C. Each alloy required an optimum reaction temperature and exhibited a particular microstructure according to the composition. The second stage of the work involved the characterization, for each temperature, of the Pr 14 Fe 80 B 6 HDDR powder processed using X-ray diffraction analysis. The samples of the HDDR material were studied by synchrotron radiation powder diffraction using the Rietveld method for cell refinement, phase quantification and crystallite sizes determination. Scanning electron microscopy has also been employed to reveal the morphology of the HDDR powder. (author)

  2. To the reaction of silyl radicals. The ratio of disproportionation/recombination

    Reimann, B.; Matten, A.; Laupert, R.; Potzinger, P.

    1977-01-01

    Silyl radicals react in two distinct ways: (1) recombination to a vibrationally highly excited disilane, and (2) disproportionation to silylene and silane. Silylene disappears by a very fast insertion reaction in which disilane is formed. - Both reaction paths (1) and (2) can be distinguished by isotopic labelling. Disilane formed by (1), either undergoes unimolecular decomposition forming silylene and silane or it is stabilized through collisions. The ratio of disproportionation to recombination products is therefore pressure dependent. The disproportionation to recombination ratio, as calculated by extrapolation to infinite pressure, is 0.7 +- 0.1. - Photoionization mass spectrometry has been applied for the quantitative analysis of the deuterated disilanes. (orig.) [de

  3. Charge disproportionation in Fe/sup 4 + -/oxides with perovskite-type structures

    Takano, M; Nakanishi, N [Konan Univ., Kobe (Japan). Faculty of Science; Takeda, Y; Naka, S [Nagoya Univ. (Japan)

    1979-01-01

    For a further examination and elaboration of our simple charge disproportionation model for Fe/sup 4 +/-oxides, 2Fe/sup 4 +/..-->..Fe/sup 3 +/ + Fe/sup 5 +/, two series of solid solutions Casub(1-x)Srsub(x)FeO/sub 3/ and Srsub(1-x)Lasub(x)FeO/sub 3/ with the perovskite structure have been studied. The Moessbauer spectrum of Srsub(0,5)Lasub(0.5)FeO/sub 3/ at 4 K clearly indicates the disproportionation. For both series of oxides, the disproportionation seems to set in at the Tsub(N).

  4. Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

    Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf [Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz (Austria)

    2014-05-14

    Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

  5. Adsorption/desorption of biomacromolecules involved in catalytic hydrogen evolution

    Strmečki, S.; Paleček, Emil

    2018-01-01

    Roč. 120, APR2018 (2018), s. 87-93 ISSN 1567-5394 R&D Projects: GA ČR(CZ) GA15-15479S Institutional support: RVO:68081707 Keywords : surface-active substances * free electrochemical analysis * mercury-electrodes Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 3.346, year: 2016

  6. Hydrogen absorption/desorption characteristics of room temperature ...

    Administrator

    mising light weight hydrides such as NaAlH4 (5\\5 wt.%) and MgH2 (7\\6 wt. ... high performance STP system with ~ 1\\5 wt.% reversible ... Ni–H is weaker than the bonding of both Zr–H and Mn– ... technique and the size of crystallites was calculated using. Scherror ... 2007) along with a smaller amount of Zr7Ni10 alloy (Yang.

  7. Positron annihilation study of hydrogen storage alloys

    Shirai, Yasuharu; Araki, Hideki; Sakaki, Kouji

    2003-01-01

    Some AB 5 and AB 2 hydrogen storage alloys have been characterized by using positron-annihilation lifetime spectroscopy. It has been shown that they contain no constitutional vacancies and that deviations from the stoichiometric compositions are all compensated by antistructure atoms. Positron lifetimes in fully-annealed LaNi 5-x Al x and MmNi 5-x Al x alloys show good correlation with their hydrogen desorption pressures. On the other hand, surprising amounts of vacancies together with dislocations have been found to be generated during the first hydrogen absorption process of LaNi 5 and ZrMn 2 . These lattice defects play important role in hydrogen absorption-desorption processes of hydrogen storage alloys. (author)

  8. Insights into the photochemical disproportionation of transition metal dimers on the picosecond time scale.

    Lomont, Justin P; Nguyen, Son C; Harris, Charles B

    2013-05-09

    The reactivity of five transition metal dimers toward photochemical, in-solvent-cage disproportionation has been investigated using picosecond time-resolved infrared spectroscopy. Previous ultrafast studies on [CpW(CO)3]2 established the role of an in-cage disproportionation mechanism involving electron transfer between 17- and 19-electron radicals prior to diffusion out of the solvent cage. New results from time-resolved infrared studies reveal that the identity of the transition metal complex dictates whether the in-cage disproportionation mechanism can take place, as well as the more fundamental issue of whether 19-electron intermediates are able to form on the picosecond time scale. Significantly, the in-cage disproportionation mechanism observed previously for the tungsten dimer does not characterize the reactivity of four out of the five transition metal dimers in this study. The differences in the ability to form 19-electron intermediates are interpreted either in terms of differences in the 17/19-electron equilibrium or of differences in an energetic barrier to associative coordination of a Lewis base, whereas the case for the in-cage vs diffusive disproportionation mechanisms depends on whether the 19-electron reducing agent is genuinely characterized by 19-electron configuration at the metal center or if it is better described as an 18 + δ complex. These results help to better understand the factors that dictate mechanisms of radical disproportionation and carry implications for radical chain mechanisms.

  9. The transformation of inorganic sulfur compounds and the assimilation of organic and inorganic carbon by the sulfur disproportionating bacterium Desulfocapsa sulfoexigens.

    Frederiksen, Trine-Maria; Finster, Kai

    2004-02-01

    The physiology of the sulfur disproportionator Desulfocapsa sulfoexigens was investigated in batch cultures and in a pH-regulated continuously flushed fermentor system. It was shown that a sulphide scavanger in the form of ferric iron was not obligatory and that the control of pH allowed production of more biomass than was possible in carbonate buffered but unregulated batch cultures. Small amounts of sulphite were produced during disproportionation of elemental sulfur and thiosulphate. In addition, it was shown that in the presence of hydrogen, a respiratory type of process is favored before the disproportionation of sulphite, thiosulphate and elemental sulfur. Sulphate reduction was not observed. D. sulfoexigens assimilated inorganic carbon even in the presence of organic carbon sources. Inorganic carbon assimilation was probably catalyzed by the reverse CO-dehydrogenase pathway, which was supported by the constitutive expression of the gene encoding CO-dehydrogenase in cultures grown in the presence of acetate and by the high carbon fractionation values that are indicative of this pathway.

  10. Formation of H- ions via vibrational excited molecules produced from recombinative wall desorption of H atoms in a low-pressure H/sub 2/ positive column

    Amorim, J.; Loureiro, J.; Schram, D.C.

    2001-01-01

    Recombinative wall desorption of hydrogen atoms in a low-pressure hydrogen positive column leading to formation of H/sub 2/ (X/sup 1/ Sigma /sub g//sup +/, v) molecules in optimum levels for H/sup -/ production by dissociative attachment is investigated. We employed a kinetic model that solves the

  11. Electron microscopy studies of materials used for hydrogen storage

    Andrei, Carmen M.

    2004-07-01

    Concerns over global warming and air pollution have stimulated the concept of the ''Hydrogen Economy'' and the potential extensive use of hydrogen as an energy carrier. Hydrogen storage in a solid matrix has become one of the promising solutions for vehicular applications. In this study, several transmission electron microscopy (TEM) techniques such as high resolution (HR), electron diffraction, energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFT EM) as well as scanning electron microscopy (SEM) have been used to study the microstructure of materials related to hydrogen storage applications. Some of the results are compared with powder X-ray diffraction (PXD) data. A TbNiAl compound processed by the hydrogenation-disproportionation-desorption-recombination (HDDR) route has been studied using a combination of SEM, TEM and PXD. Information about the variations in the composition and surface topography in both disproportionation and recombination stages is given by the SEM backscattered electrons and secondary electrons images. The crystallites that have undergone the recombination process were found smaller in size. The sodium alanate, NaAIH4 is one of the most promising candidate materials for hydrogen storage. Ti additives are effective at reducing the reaction temperatures and improving the efficiency of the kinetics. The microstructure of NaAlH4 with TiF3 additive has been examined after the initial ball milling and after 15 cycles, using TEM, SEM and EDS. The effect of the additive on particle morphology, grain size and distribution of the phases has been studied. The additive has uneven distribution in the sample after initial ball milling. After 15 cycles, EDS maps show some combination of Ti with the alanate phase. No significant change in grain size of the Na/Al rich particles between the ball milled and 15 cycled sample was observed. The LiAlD4

  12. Dependence of hydrogen-induced lattice defects and hydrogen embrittlement of cold-drawn pearlitic steels on hydrogen trap state, temperature, strain rate and hydrogen content

    Doshida, Tomoki; Takai, Kenichi

    2014-01-01

    The effects of the hydrogen state, temperature, strain rate and hydrogen content on hydrogen embrittlement susceptibility and hydrogen-induced lattice defects were evaluated for cold-drawn pearlitic steel that absorbed hydrogen in two trapping states. Firstly, tensile tests were carried out under various conditions to evaluate hydrogen embrittlement susceptibility. The results showed that peak 2 hydrogen, desorbed at temperatures above 200 °C as determined by thermal desorption analysis (TDA), had no significant effect on hydrogen embrittlement susceptibility. In contrast, hydrogen embrittlement susceptibility increased in the presence of peak 1 hydrogen, desorbed from room temperature to 200 °C as determined by TDA, at temperatures higher than −30 °C, at lower strain rates and with higher hydrogen content. Next, the same effects on hydrogen-induced lattice defects were also evaluated by TDA using hydrogen as a probe. Peak 2 hydrogen showed no significant effect on either hydrogen-induced lattice defects or hydrogen embrittlement susceptibility. It was found that hydrogen-induced lattice defects formed under the conditions where hydrogen embrittlement susceptibility increased. This relationship indicates that hydrogen embrittlement susceptibility was higher under the conditions where the formation of hydrogen-induced lattice defects tended to be enhanced. Since hydrogen-induced lattice defects formed by the interaction between hydrogen and strain were annihilated by annealing at a temperature of 200 °C, they were presumably vacancies or vacancy clusters. One of the common atomic-level changes that occur in cold-drawn pearlitic steel showing higher hydrogen embrittlement susceptibility is the formation of vacancies and vacancy clusters

  13. Hydrogen energy

    2005-03-01

    This book consists of seven chapters, which deals with hydrogen energy with discover and using of hydrogen, Korean plan for hydrogen economy and background, manufacturing technique on hydrogen like classification and hydrogen manufacture by water splitting, hydrogen storage technique with need and method, hydrogen using technique like fuel cell, hydrogen engine, international trend on involving hydrogen economy, technical current for infrastructure such as hydrogen station and price, regulation, standard, prospect and education for hydrogen safety and system. It has an appendix on related organization with hydrogen and fuel cell.

  14. Modeling Adsorption-Desorption Processes at the Intermolecular Interactions Level

    Varfolomeeva, Vera V.; Terentev, Alexey V.

    2018-01-01

    Modeling of the surface adsorption and desorption processes, as well as the diffusion, are of considerable interest for the physical phenomenon under study in ground tests conditions. When imitating physical processes and phenomena, it is important to choose the correct parameters to describe the adsorption of gases and the formation of films on the structural materials surface. In the present research the adsorption-desorption processes on the gas-solid interface are modeled with allowance for diffusion. Approaches are proposed to describe the adsorbate distribution on the solid body surface at the intermolecular interactions level. The potentials of the intermolecular interaction of water-water, water-methane and methane-methane were used to adequately modeling the real physical and chemical processes. The energies calculated by the B3LYP/aug-cc-pVDZ method. Computational algorithms for determining the average molecule area in a dense monolayer, are considered here. Differences in modeling approaches are also given: that of the proposed in this work and the previously approved probabilistic cellular automaton (PCA) method. It has been shown that the main difference is due to certain limitations of the PCA method. The importance of accounting the intermolecular interactions via hydrogen bonding has been indicated. Further development of the adsorption-desorption processes modeling will allow to find the conditions for of surface processes regulation by means of quantity adsorbed molecules control. The proposed approach to representing the molecular system significantly shortens the calculation time in comparison with the use of atom-atom potentials. In the future, this will allow to modeling the multilayer adsorption at a reasonable computational cost.

  15. Hydrogen storage development

    Thomas, G.J.; Guthrie, S.E. [Sandia National Labs., Livermore, CA (United States)

    1998-08-01

    A summary of the hydride development efforts for the current program year (FY98) are presented here. The Mg-Al-Zn alloy system was studied at low Zn levels (2--4 wt%) and midrange Al contents (40--60 wt%). Higher plateau pressures were found with Al and Zn alloying in Mg and, furthermore, it was found that the hydrogen desorption kinetics were significantly improved with small additions of Zn. Results are also shown here for a detailed study of the low temperature properties of Mg{sub 2}NiH{sub 4}, and a comparison made between conventional melt cast alloy and the vapor process material.

  16. Generation of nanopores during desorption of NH3 from Mg(NH3)6Cl2

    Hummelshøj, Jens Strabo; Sørensen, Rasmus Zink; Kostova, M.Y.

    2006-01-01

    It is shown that nanopores are formed during desorption of NH3 from Mg(NH3)6Cl2, which has been proposed as a hydrogen storage material. The system of nanopores facilitates the transport of desorbed ammonia away from the interior of large volumes of compacted storage material. DFT calculations sh...

  17. Release enhancement of tritium from graphite by addition of hydrogen

    Saeki, Masakatsu; Masaki, N.M.

    1989-01-01

    The release behavior of tritium from graphite was studied in pure He and He + H 2 atmosphere. The release from powdered graphite was significantly enhanced in hydrogen environment. Apparent diffusion coefficients of tritium in graphite also became much higher in an atmosphere containing hydrogen than values obtained in pure helium atmosphere. A careful investigation of the release processes resulted in the conclusion that the most important process of tritium behaviour in graphite was diffusion, but the desorption process of tritium from the surface played a significant role. The enhancement of the desorption process was controlled by atomic hydrogen. (orig.)

  18. The potential role of stated preference methods in the Water Framework Directive to assess disproportionate costs

    Brouwer, R.

    2008-01-01

    This paper examines the issue of disproportionate costs of Water Framework Directive (WFD) implementation using public surveys as a means to inform policy and decision making. Public taxpayers are asked their opinion regarding the implementation of the WFD and its costs. Taxpayers are expected to

  19. Disproportionation of the calcium salt of atorvastatin in the presence of acidic excipients

    Christensen, Niels Peter Aae; Rantanen, Jukka; Cornett, Claus

    2012-01-01

    The aim of the present study was to combine vibrational spectroscopy and chemometrics for investigating excipient-induced disproportionation of the calcium salt of atorvastatin into the corresponding free acid form in environments relevant to manufacturing and storage of solid dosage formulations...

  20. 78 FR 28551 - Medicaid Program; State Disproportionate Share Hospital Allotment Reductions

    2013-05-15

    ... DEPARTMENT OF HEALTH AND HUMAN SERVICES Centers for Medicare & Medicaid Services 42 CFR Part 447 [CMS-2367-P] RIN 0938-AR31 Medicaid Program; State Disproportionate Share Hospital Allotment Reductions AGENCY: Centers for Medicare & Medicaid Services (CMS), HHS. ACTION: Proposed rule. SUMMARY: The statute...

  1. 78 FR 57293 - Medicaid Program; State Disproportionate Share Hospital Allotment Reductions

    2013-09-18

    ... DEPARTMENT OF HEALTH AND HUMAN SERVICES Centers for Medicare & Medicaid Services 42 CFR Part 447 [CMS-2367-F] RIN 0938-AR31 Medicaid Program; State Disproportionate Share Hospital Allotment Reductions AGENCY: Centers for Medicare & Medicaid Services (CMS), HHS. ACTION: Final rule. SUMMARY: The statute, as...

  2. Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron or manganese

    Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler

    1993-01-01

    and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S was microbially disproportionated to sulfate and sulfide, as follows: 4S + 4H(2)O --> SO(4) + 3H(2)S + 2H. Subsequent chemical reactions between...... reduction of MnO(2) to Mn. Growth of small rod-shaped bacteria was observed. When incubated without MnO(2), the culture did not grow but produced small amounts of SO(4) and H(2)S at a ratio of 1:3, indicating again a disproportionation of S. The observed microbial disproportionation of S only proceeds...... significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S disproportionation in the presence of FeOOH or MnO(2) was high, > 10 cm in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic...

  3. Sulfur and Oxygen Isotope Fractionation During Bacterial Sulfur Disproportionation Under Anaerobic Haloalkaline Conditions

    Poser, Alexander; Vogt, Carsten; Knöller, Kay; Sorokin, Dimitry Y.; Finster, Kai W.; Richnow, Hans H.

    2016-01-01

    Sulfur and oxygen isotope fractionation of elemental sulfur disproportionation at anaerobic haloalkaline conditions was evaluated for the first time. Isotope enrichment factors of the strains Desulfurivibrio alkaliphilus and Dethiobacter alkaliphilus growing at pH 9 or 10 were −0.9‰ to −1‰ for

  4. 78 FR 45217 - Medicaid Program; Disproportionate Share Hospital Allotments and Institutions for Mental Diseases...

    2013-07-26

    ... states may make to institutions for mental diseases (IMDs) and other mental health facilities. This... DSH payments to institutions for mental diseases (IMDs) and other mental health facilities is limited... 0938-AR91 Medicaid Program; Disproportionate Share Hospital Allotments and Institutions for Mental...

  5. Do More Powerful Interest Groups have a Disproportionate Influence on Policy?

    Z. Sharif (Zara); O.H. Swank (Otto)

    2012-01-01

    textabstractDecisions-makers often rely on information supplied by interested parties. In practice, some parties have easier access to information than other parties. In this light, we examine whether more powerful parties have a disproportionate influence on decisions. We show that more powerful

  6. Ionic Adsorption and Desorption of CNT Nanoropes

    Jun-Jun Shang

    2016-09-01

    Full Text Available A nanorope is comprised of several carbon nanotubes (CNTs with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

  7. Hydrogen storage in complex hydrides

    Lupu, D.; Biris, A. R.; Misan, I.

    2005-01-01

    Full text: Hydrogen storage is a key enabling technology for the advancement of hydrogen and fuel cell power technologies in mobile and stationary applications. A relevant role of the fuel cell powered vehicles on the market of the transportation systems will be achieved only if the research and development of on-board vehicular hydrogen storage are able to allow a driving range of at least 500 km. The on-board hydrogen storage systems are more challenging due to the space, weight and cost limitations. This range of autonomy between refueling requires materials able to store at least 6.5% weight hydrogen, available at moderate pressures, at the working temperature of the fuel cells and with acceptable cycling stability. The intensive research on the hydrogen storage in alloys and intermetallic of the LaNi 5 , FeTi or Laves phase type compounds, which started more than three decades ago did not resulted in materials of more than about 3% H storage capacities. The 7.5% H content of the Mg hydride is still of attracting interest but though the absorption has been achieved at lower temperatures by ball milling magnesium with various amounts of nickel, the desorption can not be attained at 1 bar H 2 below 280 deg. C and the kinetics of the process is too slow. In the last decade, the attention is focused on another class of compounds, the complex hydrides of aluminum with alkali metals (alanates), due to their high hydrogen content. It was found that doping with Ti-based catalysts improve the hydrogenation/dehydrogenation conditions of NaAlH 4 . Later on, it was shown that ball milling with solid state catalysts greatly improve the hydrogen desorption kinetics of NaAlH 4 , and this also helps to the rehydriding process. The hydrogen desorption from NaAlH 4 occurs in three steps, it shows a reversible storage capacity of 5.5% H and this led to further research work for a better knowledge of its application relating properties. In this work, ball milling experiments on Na

  8. Theoretical study of hydrogen storage in metal hydrides.

    Oliveira, Alyson C M; Pavão, A C

    2018-05-04

    Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

  9. Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

    Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

    2006-03-07

    The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

  10. Interaction of hydrogen and its isotopes with irradiated beryllium

    Tazhibaeva, I.L.; Shestakov, V.P.; Klepikov, A.Kh.; Pomanenko, O.G.; Chikhraj, E.V.; Kenzhin, E.A.; Zverev, V.V.; Kolbanenkov, A.N.

    2000-01-01

    In the article the results of experiments on hydrogen and its isotopes accumulation and gas-release from irradiated beryllium are presented. The irradiation was conducted at different media and temperatures in the RA and IVG.1M reactors. The measurements were carried out by thermal desorption method. Hydrogen release from beryllium samples saturated at different conditions were calculated. Dependence of hydrogen confinement character in beryllium from grain orientation in the sample, temperature and irradiation rate was revealed

  11. Ageing of Mg-Ni-H hydrogen storage alloys

    Čermák, Jiří; Král, Lubomír

    2012-01-01

    Roč. 37, OCT (2012), s. 14257-14264 ISSN 0360-3199 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA ČR GA106/09/0814; GA ČR(CZ) GAP108/11/0148 Institutional research plan: CEZ:AV0Z20410507 Keywords : Magnesium alloys * Hydrogen desorption * Hydrogen storage * Hydrogen-storage materials * Ageing Subject RIV: JG - Metallurgy Impact factor: 3.548, year: 2012

  12. Hydrogen retention properties of polycrystalline tungsten and helium irradiated tungsten

    Hino, T.; Koyama, K.; Yamauchi, Y.; Hirohata, Y.

    1998-01-01

    The hydrogen retention properties of a polycrystalline tungsten and tungsten irradiated by helium ions with an energy of 5 keV were examined by using an ECR ion irradiation apparatus and a technique of thermal desorption spectroscopy, TDS. The polycrystalline tungsten was irradiated at RT with energetic hydrogen ions, with a flux of 10 15 H cm -2 and an energy of 1.7 keV up to a fluence of 5 x 10 18 H cm -2 . Subsequently, the amount of retained hydrogen was measured by TDS. The heating temperature was increased from RT to 1000 C, and the heating rate was 50 C min -1 . Below 1000 C, two distinct hydrogen desorption peaks were observed at 200 C and 400 C. The retained amount of hydrogen was observed to be five times smaller than that of graphite, but the concentration in the implantation layer was comparable with that of graphite. Also, the polycrystalline tungsten was irradiated with 5 keV helium ions up to a fluence of 1.4 x 10 18 He cm -2 , and then re-irradiated with 1.7 keV hydrogen ions. The amount of retained hydrogen in this later experiment was close to the value in the case without prior helium ion irradiation. However, the amount of hydrogen which desorbed around the low temperature peak, 200 C, was largely enhanced. The desorption amount at 200 C saturated for the helium fluence of more than 5 x 10 17 He cm -2 . The present data shows that the trapping state of hydrogen is largely changed by the helium ion irradiation. Additionally, 5 keV helium ion irradiation was conducted on a sample pre-implanted with hydrogen ions to simulate a helium ion impact desorption of hydrogen retained in tungsten. The amount of the hydrogen was reduced as much as 50%. (orig.)

  13. The self-disproportionation of enantiomers (SDE): a menace or an opportunity?

    Han, Jianlin; Kitagawa, Osamu; Wzorek, Alicja; Klika, Karel D; Soloshonok, Vadim A

    2018-02-21

    Herein we report on the well-documented, yet not widely known, phenomenon of the self-disproportionation of enantiomers (SDE): the spontaneous fractionation of scalemic material into enantioenriched and -depleted fractions when any physicochemical process is applied. The SDE has implications ranging from the origins of prebiotic homochirality to unconventional enantiopurification methods, though the risks of altering the enantiomeric excess (ee) unintentionally, regrettably, remain greatly unappreciated. While recrystallization is well known as an SDE process, occurrences of the SDE in other processes are much less recognized, e.g. sublimation and even distillation. But the most common process that many workers seem to be completely ignorant of is SDE via chromatography and reports have included all manner of structures, all types of interactions, and all forms of chromatography, including GC. The SDE can be either a blessing - as a means to obtain enantiopure samples from scalemates - or a curse, as unwitting alteration of the ee leads to errors in the reporting of results and/or misinterpretation of the system under study. Thus the ramifications of the SDE are relevant to any area involving chirality - natural products, asymmetric synthesis, etc. Moreover, there is grave concern regarding errors in the literature, in addition to the possible occurrence of valid results which may have been overlooked and thus remain unreported, as well as the potential for the SDE to alter the ee, particularly via chromatography, and the following concepts will be conveyed: (1) the SDE occurs under totally achiral conditions of (a) precipitation, (b) centrifugation, (c) evaporation, (d) distillation, (e) crystallization, (f) sublimation, and (g) achiral chromatography ( e.g. column, flash, MPLC, HPLC, SEC, GC, etc. ). (2) The SDE cannot be controlled simply by experimental accuracy and ignorance of the SDE unavoidably leads to mistakes in the recorded and reported stereochemical

  14. Surface Structures and Thermal Desorption Behaviors of Cyclopentanethiol Self-Assembled Monolayers on Au(111)

    Kang, Hun Gu; Kim, You Young; Park, Tae Sun; Noh, Jae Geun [Hanyang University, Seoul (Korea, Republic of); Park, Joon B. [Chonbuk National University, Jeonju (Korea, Republic of); Ito, Eisuke; Hara, Masahiko [RIKEN-HYU Collaboration Center, Saitama (Japan)

    2011-04-15

    The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at 50 .deg. C formed well-ordered SAMs with a (2√3 x √5)R41{sup .}deg. packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments (C{sub 5}H{sub 9} {sup +}, m/e = 69) generated via C-S bond cleavage and the parent molecular species (C{sub 5}H{sub 9}SH{sup +}, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.

  15. Surface Structures and Thermal Desorption Behaviors of Cyclopentanethiol Self-Assembled Monolayers on Au(111)

    Kang, Hun Gu; Kim, You Young; Park, Tae Sun; Noh, Jae Geun; Park, Joon B.; Ito, Eisuke; Hara, Masahiko

    2011-01-01

    The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at 50 .deg. C formed well-ordered SAMs with a (2√3 x √5)R41".deg. packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments (C_5H_9 "+, m/e = 69) generated via C-S bond cleavage and the parent molecular species (C_5H_9SH"+, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs

  16. Secondary ion shadow-cone enhanced desorption

    Chechen Chang (Hawaii Univ., Honolulu (USA). Dept. of Chemistry)

    1990-02-01

    The incident angle dependence of the secondary particle emission process under keV ion bombardment has been investigated. The results from the full molecular dynamics calculations indicate that the flux anisotropy of the incident beam, resulting from the non-uniform impact parameters for the surface atom of a single crystal, affects the particle desorption in a systematic fashion. The enhanced desorption at certain angles of incidence corresponds to the intensive focusing of the incident beam to the near-surface atom and the extended dissipation of momentum by large-angle scattering. This observation has let us to develop a new theoretical model in which the enhanced desorption is described by the distance of closest encounter along the trajectory of the incident particle to the surface atom. The computer time for the simulation of the incident-angle-dependent emission process is significantly reduced. The results from the calculation based on this model are in good agreement both with the results from the full dynamics calculation and with the experimental results. The new model also allows a complementary evaluation of the microscopic dynamics involved in the shadow-cone enhanced desorption. (author).

  17. Hydrogenation properties and microstructure of Ti-Mn-based alloys for hybrid hydrogen storage vessel

    Shibuya, Masachika; Nakamura, Jin; Akiba, Etsuo

    2008-01-01

    Ti-Mn-based AB 2 -type alloys which are suitable for a hybrid hydrogen storage vessel have been synthesized and evaluated hydrogenation properties. As the third element V was added to Ti-Mn binary alloys. All the alloys synthesized in this work mainly consist of the C14 Laves and BCC phase. In the case of Ti0.5V0.5Mn alloy, the amounts of hydrogen absorption was 1.8 wt.% at 243 K under the atmosphere of 7 MPa H 2 , and the hydrogen desorption pressure was in the range of 0.2-0.4 MPa at 243 K. The hydrogen capacity of this alloy did not saturate under 7 MPa H 2 and seems to increase with hydrogen pressure up to 35 MPa that is estimated working pressure of the hybrid hydrogen storage vessel

  18. Exciton-Promoted Desorption From Solid Water Surfaces A2

    McCoustra, M.R.S.; Thrower, J.D.

    2018-01-01

    Abstract Desorption from solid water surfaces resulting from interaction with electromagnetic and particle radiation is reviewed in the context of the role of nonthermal desorption in astrophysical environments. Experimental observations are interpreted in terms of mechanisms sharing a common basis...

  19. Prospects for hydrogen storage in graphene.

    Tozzini, Valentina; Pellegrini, Vittorio

    2013-01-07

    Hydrogen-based fuel cells are promising solutions for the efficient and clean delivery of electricity. Since hydrogen is an energy carrier, a key step for the development of a reliable hydrogen-based technology requires solving the issue of storage and transport of hydrogen. Several proposals based on the design of advanced materials such as metal hydrides and carbon structures have been made to overcome the limitations of the conventional solution of compressing or liquefying hydrogen in tanks. Nevertheless none of these systems are currently offering the required performances in terms of hydrogen storage capacity and control of adsorption/desorption processes. Therefore the problem of hydrogen storage remains so far unsolved and it continues to represent a significant bottleneck to the advancement and proliferation of fuel cell and hydrogen technologies. Recently, however, several studies on graphene, the one-atom-thick membrane of carbon atoms packed in a honeycomb lattice, have highlighted the potentialities of this material for hydrogen storage and raise new hopes for the development of an efficient solid-state hydrogen storage device. Here we review on-going efforts and studies on functionalized and nanostructured graphene for hydrogen storage and suggest possible developments for efficient storage/release of hydrogen under ambient conditions.

  20. Repression of both isoforms of disproportionating enzyme leads to higher malto-oligosaccharide content and reduced growth in potato

    Mogensen, Henrik Lütken; Lloyd, James Richard; Glaring, Mikkel A.

    2010-01-01

    Two glucanotransferases, disproportionating enzyme 1 (StDPE1) and disproportionating enzyme 2 (StDPE2), were repressed using RNA interference technology in potato, leading to plants repressed in either isoform individually, or both simultaneously. This is the first detailed report of their combin...

  1. Hydrogen sensor

    Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

    2010-11-23

    A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

  2. Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese

    Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm

    1993-01-01

    A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835

  3. Visualization of hydrogen in steels by secondary ion mass spectrometry

    Takai, Kenichi

    2000-01-01

    Secondary ion mass spectrometry (SIMS) enables us to visualize hydrogen trapping sites in steels. Information about the hydrogen trapping sites in high-strength steels by SIMS is very important to discuss environmental embrittlement mechanism for developing steels with a high resistance to the environmental embrittlement. Secondary ion image analysis by SIMS has made possible to visualize the hydrogen and deuterium trapping sites in the steels. Hydrogen in tempered martensite steels containing Ca tends to accumulate on inclusions, at grain boundaries, and in segregation bands. Visualization of hydrogen desorption process by secondary ion image analysis confirms that the bonding between the inclusions and the hydrogen is strong. Cold-drawn pearlite steels trap hydrogen along cold-drawing direction. Pearlite phase absorbs the hydrogen more than ferrite phase does. This article introduces the principle of SIMS, its feature, analysis method, and results of hydrogen visualization in steels. (author)

  4. Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption.

    Fukushi, Keisuke; Sakai, Haruka; Itono, Taeko; Tamura, Akihiro; Arai, Shoji

    2014-09-16

    Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs(+) desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca(2+) and Mg(2+) (>0.5 mM) and high concentrations of K(+). The order of ability for Cs desorption was Na(+) = K(+) > Ca(2+) = Mg(2+) at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs(+) desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments.

  5. Report on the results of the FY 1998 hydrogen utilization international clean energy system technology (WE-NET). Subtask 5. Survey on the R and D of technologies for hydrogen transport and storage by hydrogen absorbing alloys (V. Development of the distributed transport/storage use hydrogen absorbing alloys); 1998 nendo suiso riyo kokusai clean energy system gijutsu (WE-NET). 5. Suiso yuso chozo gijutsu no kaihatsu (V. bunsan yuso chozoyo suiso kyuzo gokin no kaihatsu)

    NONE

    1999-03-01

    The paper described the FY 1998 results of the development of hydrogen distributed transport/storage use absorbing alloys in the WE-NET project. Study was made of improvement of hydrogen desorption characteristics by substituting Ca for part of Mg of Mg-Ni alloys and substituting Cr for part of Ni. It is necessary to shift the state of atomic bond by H atom and metal atom in alloys from the ionic bond to the metallic bond, and to change from the amorphous state to the BCC type crystal structure. It was found out that it was possible to do it by improving the composition and heat treatment. The addition of Cu to LaMg{sub 2} alloys shifts the bond with hydrogen to the bond with metal. Easy hydrogen desorption and large absorbing capacity can be expected. It was found out that LaMg{sub 2}Cu{sub 2} synthesized by the reaction sintering method has reversible hydrogen absorbing desorption characteristics. The absorbing amount is 2.4 wt%, the desorption amount 1.2 wt%, and the desorption temperature 190 degrees C. Those are still far from WE-NET targeted values, but a clue to the search was obtained. It was found out that by applying doping technology by Ti, etc. to NaAlH{sub 4}, characteristics can be expected of the desorption amount, 4.5 wt%, of the hydrogen desorption starting temperature from 100 degrees C to 200 degrees C. (NEDO)

  6. Radiation-electrochemistry of the colloidal gold micro-electrode: Hydrogen formation by organic free radicals

    Westerhausen, J.; Henglein, A.; Lilie, J.

    1981-01-01

    Various organic free radicals as well as Ni + ions produce hydrogen in the presence of some 10 -4 M of colloidal gold. The gold catalyst was prepared via the reduction of HAuCl 4 either thermally by citrate or by γ-irradiation. The organic radicals were radiolytically produced. The mechanism of H 2 formation includes electron transfer from the organic radicals to the gold particles, storage of a large number of electrons per gold particle, conversion of the electrons into adsorbed H-atoms and desorption of the latter to form H 2 . - The rates of some of these steps were measured using the method of pulse radiolysis. 1-Hydroxy-1-methyl ethyl radicals, (CH 3 ) 2 COH, react with colloidal gold particles almost diffusion controlled provided that the gold particles are not charged with excess electrons. Charged gold particles react at a substantially lower rate. The stored electrons live seconds or even minutes depending on their number per gold particle. In the stationary state, up to 0.38 Coulomb of electrons could be stored per liter of a 2.9x10 -4 molar gold solution, each gold particle carrying about 39 electrons. A comparison is also made between the catalytic activities of colloidal gold and silver. Due to the relative fast conversion of electrons into adsorbed H-atoms, colloidal gold has less capacity for the storage of electrons than colloidal silver. - The dependence of the hydrogen yield on the pH of the solution, the concentration of gold, the size of the gold particles, the concentration of the polyvinyl alcohol stabilizer, and the intensity of radiation was also investigated. At high intensities, some of the radicals are destroyed in a gold catalysed disproportionation. (orig.)

  7. Hydrogen system (hydrogen fuels feasibility)

    Guarna, S.

    1991-07-01

    This feasibility study on the production and use of hydrogen fuels for industry and domestic purposes includes the following aspects: physical and chemical properties of hydrogen; production methods steam reforming of natural gas, hydrolysis of water; liquid and gaseous hydrogen transportation and storage (hydrogen-hydride technology); environmental impacts, safety and economics of hydrogen fuel cells for power generation and hydrogen automotive fuels; relevant international research programs

  8. The Role of Hydrogen-Enhanced Strain-Induced Lattice Defects on Hydrogen Embrittlement Susceptibility of X80 Pipeline Steel

    Hattori, M.; Suzuki, H.; Seko, Y.; Takai, K.

    2017-08-01

    Studies to date have not completely determined the factors influencing hydrogen embrittlement of ferrite/bainite X80 pipeline steel. Hydrogen embrittlement susceptibility was evaluated based on fracture strain in tensile testing. We conducted a thermal desorption analysis to measure the amount of tracer hydrogen corresponding to that of lattice defects. Hydrogen embrittlement susceptibility and the amount of tracer hydrogen significantly increased with decreasing crosshead speed. Additionally, a significant increase in the formation of hydrogen-enhanced strain-induced lattice defects was observed immediately before the final fracture. In contrast to hydrogen-free specimens, the fracture surface of the hydrogen-charged specimens exhibited shallower dimples without nuclei, such as secondary phase particles. These findings indicate that the presence of hydrogen enhanced the formation of lattice defects, particularly just prior to the occurrence of final fracture. This in turn enhanced the formation of shallower dimples, thereby potentially causing premature fracture of X80 pipeline steel at lower crosshead speeds.

  9. Electron Stimulated Molecular Desorption of a NEG St 707 at Room Temperature

    Le Pimpec, F; Laurent, Jean Michel

    2001-01-01

    Electron stimulated molecular desorption (ESD) from a NEG St 707 (SAES GettersTM) sample after conditioning and after saturation with isotopic carbon monoxide2,13C18O, has been studied on a laboratory setup. Measurements were performed using an electron beam of 300 eV kinetic energy, with an average electron intensity of 1.6 1015 electrons s-1. The electrons were impinging on the 15 cm2 target surface at perpendicular incidence. It is found that the desorption yields h (molecules/electron) of the characteristic gases in an UHV system (hydrogen, methane, water, carbon monoxide, carbon dioxide) for a fully activated NEG as well as for a NEG fully saturated with 13C18O are lower than for OFHC copper baked at 120oC. A small fraction only of the gas which is required to saturate the getter surface can be re-desorbed and thus appears to be accessible to ESD.

  10. New vistas in the determination of hydrogen in aerospace engine metal alloys

    Danford, M. D.

    1986-01-01

    The application of diffusion theory to the analysis of hydrogen desorption data has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, were studied in this work. For the nickel base alloys, it was found that the hydrogen distributions after electrolytic charging conformed closely to those which would be predicted by diffusion theory. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, were essentially uniform in nature, which would not be predicted by diffusion theory. Finally, it has been found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the 'fast' hydrogen is not due to surface and subsurface hydride formation, as was originally proposed.

  11. Influence of adsorbed carbon dioxide on hydrogen electrosorption in palladium-platinum-rhodium alloys

    Lukaszewski, M.; Grden, M.; Czerwinski, A.

    2004-01-01

    Carbon dioxide electroreduction was applied to examine the processes of hydrogen electrosorption (adsorption, absorption and desorption) by thin electrodeposits of Pd-Pt-Rh alloys under conditions of cyclic voltammetric (CV) experiments. Due to different adsorption characteristics towards the adsorption product of the electroreduction of CO 2 (reduced CO 2 ) exhibited by the alloy components hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. Reduced CO 2 causes partial blocking of hydrogen adsorbed on surface Pt and Rh atoms, without any significant effect on hydrogen absorption into alloy. It reflects the fact that adsorbed hydrogen bonded to Pd atoms does not participate in CO 2 reduction, while hydrogen adsorbed on Pt and Rh surface sites is inactive in the absorption reaction. In contrast, CO is adsorbed on all alloy components and causes a marked inhibition of hydrogen sorption (both adsorption and absorption)/desorption reactions

  12. Qualitative and quantitative analysis of complex temperature-programmed desorption data by multivariate curve resolution

    Rodríguez-Reyes, Juan Carlos F.; Teplyakov, Andrew V.; Brown, Steven D.

    2010-10-01

    The substantial amount of information carried in temperature-programmed desorption (TPD) experiments is often difficult to mine due to the occurrence of competing reaction pathways that produce compounds with similar mass spectrometric features. Multivariate curve resolution (MCR) is introduced as a tool capable of overcoming this problem by mathematically detecting spectral variations and correlations between several m/z traces, which is later translated into the extraction of the cracking pattern and the desorption profile for each desorbate. Different from the elegant (though complex) methods currently available to analyze TPD data, MCR analysis is applicable even when no information regarding the specific surface reaction/desorption process or the nature of the desorbing species is available. However, when available, any information can be used as constraints that guide the outcome, increasing the accuracy of the resolution. This approach is especially valuable when the compounds desorbing are different from what would be expected based on a chemical intuition, when the cracking pattern of the model test compound is difficult or impossible to obtain (because it could be unstable or very rare), and when knowing major components desorbing from the surface could in more traditional methods actually bias the quantification of minor components. The enhanced level of understanding of thermal processes achieved through MCR analysis is demonstrated by analyzing three phenomena: i) the cryogenic desorption of vinyltrimethylsilane from silicon, an introductory system where the known multilayer and monolayer components are resolved; ii) acrolein hydrogenation on a bimetallic Pt-Ni-Pt catalyst, where a rapid identification of hydrogenated products as well as other desorbing species is achieved, and iii) the thermal reaction of Ti[N(CH 3) 2] 4 on Si(100), where the products of surface decomposition are identified and an estimation of the surface composition after the

  13. Hail hydrogen

    Hairston, D.

    1996-01-01

    After years of being scorned and maligned, hydrogen is finding favor in environmental and process applications. There is enormous demand for the industrial gas from petroleum refiners, who need in creasing amounts of hydrogen to remove sulfur and other contaminants from crude oil. In pulp and paper mills, hydrogen is turning up as hydrogen peroxide, displacing bleaching agents based on chlorine. Now, new technologies for making hydrogen have the industry abuzz. With better capabilities of being generated onsite at higher purity levels, recycled and reused, hydrogen is being prepped for a range of applications, from waste reduction to purification of Nylon 6 and hydrogenation of specialty chemicals. The paper discusses the strong market demand for hydrogen, easier routes being developed for hydrogen production, and the use of hydrogen in the future

  14. Thermal desorption study of physical forces at the PTFE surface

    Wheeler, D. R.; Pepper, S. V.

    1987-01-01

    Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possible role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

  15. Reprint of: Effects of cold deformation, electron irradiation and extrusion on deuterium desorption behavior in Zr-1%Nb alloy

    Morozov, O.; Mats, O.; Mats, V.; Zhurba, V.; Khaimovich, P.

    2018-01-01

    The present article introduces the data of analysis of ranges of ion-implanted deuterium desorption from Zr-1% Nb alloy. The samples studied underwent plastic deformation, low temperature extrusion and electron irradiation. Plastic rolling of the samples at temperature ∼300 K resulted in plastic deformation with the degree of ε = 3.9 and the formation of nanostructural state with the average grain size of d = 61 nm. The high degree of defectiveness is shown in thermodesorption spectrum as an additional area of the deuterium desorption in the temperature ranges 650-850 K. The further processing of the sample (that had undergone plastic deformation by plastic rolling) with electron irradiation resulted in the reduction of the average grain size (58 nm) and an increase in borders concentration. As a result the amount of deuterium desorpted increased in the temperature ranges 650-900 K. In case of Zr-1% Nb samples deformed by extrusion the extension of desorption area is observed towards the temperature reduction down to 420 K. The formation of the phase state of deuterium solid solution in zirconium was not observed. The structural state behavior is a control factor in the process of deuterium thermodesorption spectrum structure formation with a fixed implanted deuterium dose (hydrogen diagnostics). It appears as additional temperature ranges of deuterium desorption depending on the type, character and defect content.

  16. Thermal desorption of deuterium implanted into beryllium

    Markin, A.V.; Chernikov, V.N.; Zakharov, A.P.

    1995-01-01

    By means of TDS measurements it is shown that the desorption of deuterium from Be implanted with 5 keV D ions to fluences, Φ, from 1x10 20 D/m 2 to 1x10 21 D/m 2 proceeds in one high temperature stage B, while at Φ ≥ 1.2x10 21 D/m 2 one more stage A is added. The desorption maximum A is narrow and consists of two peaks A 1 and A 2 at about 460 K and 490 K, respectively. Peak A 1 is attributed to the desorption of deuterium from the walls of opened channels formed under D ion implantation. Peak A 2 is a consequence of the opening of a part of closed bubbles/channels to the outer surface. The position of maximum B shifts noticeably and nonsteadily on the fluence in a range from 850 to 1050 K. The origin of this maximum is the liberation of D atoms bound at vacancy complexes discussed previously by Wampler. The dependence of Tm(B) on the fluence is governed by the interaction of freely migrating D atoms with partly opened or fully closed gas cavity arrangements which are created under temperature ramping, but differently in specimens implanted with D ions to different fluences

  17. Lead sorption-desorption from organic residues.

    Duarte Zaragoza, Victor M; Carrillo, Rogelio; Gutierrez Castorena, Carmen M

    2011-01-01

    Sorption and desorption are mechanisms involved in the reduction of metal mobility and bioavailability in organic materials. Metal release from substrates is controlled by desorption. The capacity of coffee husk and pulp residues, vermicompost and cow manure to adsorb Pb2+ was evaluated. The mechanisms involved in the sorption process were also studied. Organic materials retained high concentrations of lead (up to 36,000 mg L(-1)); however, the mechanisms of sorption varied according to the characteristics of each material: degree of decomposition, pH, cation exchange capacity and percentage of organic matter. Vermicompost and manure removed 98% of the Pb from solution. Lead precipitated in manure and vermicompost, forming lead oxide (PbO) and lead ferrite (PbFe4O7). Adsorption isotherms did not fit to the typical Freundlich and Langmuir equations. Not only specific and non-specific adsorption was observed, but also precipitation and coprecipitation. Lead desorption from vermicompost and cow manure was less than 2%. For remediation of Pb-polluted sites, the application of vermicompost and manure is recommended in places with alkaline soils because Pb precipitation can be induced, whereas coffee pulp residue is recommended for acidic soils where Pb is adsorbed.

  18. Carbon compound used in hydrogen storage

    Iturbe G, J.L.; Lopez M, B.E.

    2004-01-01

    In the present work it is studied the activated carbon of mineral origin for the sorption of hydrogen. The carbon decreased of particle size by means of the one alloyed mechanical. The time of mill was of 10 hours. The characterization one carries out by scanning electron microscopy and X-ray diffraction. The hydrogen sipped in the carbon material it was determined using the Thermal gravimetric method (TGA). The conditions of hydrogenation went at 10 atm of pressure and ambient temperature during 18 hours. They were also carried out absorption/desorption cycles of hydrogen in the same one system of thermal gravimetric analysis. The results showed percentages of sorption of 2% approximately in the cycles carried out in the system TGA and of 4.5% in weight of hydrogen at pressure of 10 atmospheres and ambient temperature during 18 hours. (Author)

  19. Functional nanometers for hydrogen storage produced by ball milling

    Czujko, T. [Waterloo Univ., ON (Canada). Dept. of Mechanical and Mechatronics Engineering]|[Military Univ. of Technology, Warsaw (Poland). Dept. of Advanced Materials and Technologies; Varin, R.A. [Waterloo Univ., ON (Canada). Dept. of Mechanical and Mechatronics Engineering; Wronski, Z.S. [Natural Resources Canada, Ottawa, ON (Canada). CANMET Energy Technology Centre, Hydrogen Fuel Cells and Transportation; Zaranski, Z. [Military Univ. of Technology, Warsaw (Poland). Dept. of Advanced Materials and Technologies

    2008-07-01

    It is becoming increasingly important to switch to cleaner alternative energy carriers such as hydrogen, as environmental concerns over greenhouse gas emissions from the burning of fossil fuel increase. Specifically, there is a need for efficient on-board hydrogen storage technologies for vehicular applications. This paper discussed three different methods of hydrogen desorption temperature reduction and desorption kinetics of nanostructured hydrides. The first method was based on substantial hydride particle size refinement. The second method utilized catalytic effects of nanometric n-alumina (Al{sub 2}O{sub 3}), n-yttrium oxide powder (Y{sub 2}O{sub 3}) and n-nickel (Ni) additives. The third method was based on a composite of nanohydride mixtures. The composite approach was applied to the magnesium hydride (MgH{sub 2}) plus sodium tetrahydridoborate (NaBH{sub 4}) and lithium aluminum hydride (LiAlH{sub 4}) systems. The paper presented the effects of nanostructuring and nanocatalytic additives on Mg hydride desorption properties as well as a composite behaviour of nanostructured complex hydrides. It was concluded that milling of commercial MgH{sub 2} with the nano-oxide additives had a limited effect on improving the hydrogen storage properties. The addition of specialty Inco nanometric Ni reduced the hydrogen desorption temperature considerably. 28 refs., 1 tab., 9 figs.

  20. Anelastic mechanical loss spectrometry of hydrogen in austenitic stainless steels

    Yagodzinskyy, Y.; Andronova, E.; Ivanchenko, M.; Haenninen, H.

    2009-01-01

    Atomic distribution of hydrogen, its elemental diffusion jumps and its interaction with dislocations in a number of austenitic stainless steels are studied with anelastic mechanical loss (AML) spectrometry in combination with the hydrogen thermal desorption method. Austenitic stainless steels of different chemical composition, namely, AISI 310, AISI 201, and AISI 301LN, as well as LDX 2101 duplex stainless steel are studied to clarify the role of different alloying elements on the hydrogen behavior. Activation analyses of the hydrogen Snoek-like peaks are performed with their decomposition to sets of Gaussian components. Fine structure of the composite hydrogen peaks is analyzed under the assumption that each component corresponds to diffusion transfer of hydrogen between octahedral positions with certain atomic compositions of the nearest neighbouring lattice sites. An additional component originating from hydrogen-dislocation interaction is considered. Binding energies for hydrogen-dislocation interaction are also estimated for the studied austenitic stainless steels.

  1. The Impact of Medicaid Disproportionate Share Hospital Payment on Provision of Hospital Uncompensated Care

    Hsieh, Hui-Min; Bazzoli, Gloria J.

    2012-01-01

    This study examines the association between hospital uncompensated care (UC) and reductions in Medicaid Disproportionate Share Hospital (DSH) payments resulting from the 1997 Balanced Budget Act. Data on California hospitals from 1996 to 2003 were examined using two-stage least squares with a first-differencing model to control for potential feedback effects. Our findings suggest that not-for-profit hospitals did reduce UC provision in response to reductions in Medicaid DSH, but the response was inelastic in value. Policy makers need to continue to monitor how UC changes as sources of support for indigent care change with the Patient Protection and Affordable Care Act (PPACA). PMID:23230705

  2. Effects of External Hydrogen on Hydrogen Transportation and Distribution Around the Fatigue Crack Tip in Type 304 Stainless Steel

    Chen, Xingyang; Zhou, Chengshuang; Cai, Xiao; Zheng, Jinyang; Zhang, Lin

    2017-10-01

    The effects of external hydrogen on hydrogen transportation and distribution around the fatigue crack tip in type 304 stainless steel were investigated by using hydrogen microprint technique (HMT) and thermal desorption spectrometry. HMT results show that some silver particles induced by hydrogen release are located near the fatigue crack and more silver particles are concentrated around the crack tip, which indicates that hydrogen accumulates in the vicinity of the crack tip during the crack growth in hydrogen gas environment. Along with the crack propagation, strain-induced α' martensite forms around the crack tip and promotes hydrogen invasion into the matrix, which will cause the crack initiation and propagation at the austenite/ α' martensite interface. In addition, the hydrogen content in the vicinity of the crack tip is higher than that at the crack edge far away from the crack tip, which is related to the stress state and strain-induced α' martensite.

  3. Hydrogen detector

    Kumagaya, Hiromichi; Yoshida, Kazuo; Sanada, Kazuo; Chigira, Sadao.

    1994-01-01

    The present invention concerns a hydrogen detector for detecting water-sodium reaction. The hydrogen detector comprises a sensor portion having coiled optical fibers and detects hydrogen on the basis of the increase of light transmission loss upon hydrogen absorption. In the hydrogen detector, optical fibers are wound around and welded to the outer circumference of a quartz rod, as well as the thickness of the clad layer of the optical fiber is reduced by etching. With such procedures, size of the hydrogen detecting sensor portion can be decreased easily. Further, since it can be used at high temperature, diffusion rate is improved to shorten the detection time. (N.H.)

  4. Thermodesorption examination of interaction of hydrogen with traps in silver

    Gabis, I.E.; Kurdyumov, A.A.; Ovsvannikova, T.A.

    1992-01-01

    The authors have previously examined the interaction of hydrogen with silver by the methods of thermal desorption spectrometry (TDS) and hydrogen permeability. The results showed that the TDS spectra contained a high-temperature phase linked with hydrogen which left the volume of the specimen during heating. It was assumed that hydrogen was captured and released by structural defects acting as traps. These traps can be represented by vacancies and their clusters. In this work, the high-temperature desorption of hydrogen from silver was studied. The experimental setup consisted of an all-metal vacuum system, a time-of-flight mass spectrometer, a DVK-2M computing system, and a Camac system. The described model of a local equilibrium should be regarded only as a first approximation. The results provide unambiguous information on the processes of permeability and desorption, and make it possible to assume that the formation of the high-temperature phase in TD spectra was caused by the generation of hydrogen from the traps. The parameters of the interaction of hydrogen with the traps were determined by the concentration wave method. 7 refs., 2 figs

  5. Hysteresis-free nanoplasmonic pd-au alloy hydrogen sensors

    Wadell, Carl; Nugroho, Ferry Anggoro Ardy; Lidström, Emil

    2015-01-01

    hydrogen sensors. By increasing the amount of Au in the alloy nanoparticles up to 25 atom %, we are able to suppress the hysteresis between hydrogen absorption and desorption, thereby increasing the sensor accuracy to below 5% throughout the investigated 1 mbar to 1 bar hydrogen pressure range. Furthermore......, we observe an 8-fold absolute sensitivity enhancement at low hydrogen pressures compared to sensors made of pure Pd, and an improved sensor response time to below one second within the 0-40 mbar pressure range, that is, below the flammability limit, by engineering the nanoparticle size....

  6. Alloying effect on the electronic structures of hydrogen storage compounds

    Yukawa, H.; Moringa, M.; Takahashi, Y. [Nagoya Univ. (Japan). Dept. of Mater. Sci. and Eng.

    1997-05-20

    The electronic structures of hydrogenated LaNi{sub 5} containing various 3d transition elements were investigated by the DV-X{alpha} molecular orbital method. The hydrogen atom was found to form a strong chemical bond with the Ni rather than the La atoms. The alloying modified the chemical bond strengths between atoms in a small metal octahedron containing a hydrogen atom at the center, resulting in the change in the hydrogen absorption and desorption characteristics of LaNi{sub 5} with alloying. (orig.) 7 refs.

  7. A COL11A2 mutation in Labrador retrievers with mild disproportionate dwarfism.

    Mirjam Frischknecht

    Full Text Available We describe a mild form of disproportionate dwarfism in Labrador Retrievers, which is not associated with any obvious health problems such as secondary arthrosis. We designate this phenotype as skeletal dysplasia 2 (SD2. It is inherited as a monogenic autosomal recessive trait with incomplete penetrance primarily in working lines of the Labrador Retriever breed. Using 23 cases and 37 controls we mapped the causative mutation by genome-wide association and homozygosity mapping to a 4.44 Mb interval on chromosome 12. We re-sequenced the genome of one affected dog at 30x coverage and detected 92 non-synonymous variants in the critical interval. Only two of these variants, located in the lymphotoxin A (LTA and collagen alpha-2(XI chain gene (COL11A2, respectively, were perfectly associated with the trait. Previously described COL11A2 variants in humans or mice lead to skeletal dysplasias and/or deafness. The dog variant associated with disproportionate dwarfism, COL11A2:c.143G>C or p.R48P, probably has only a minor effect on collagen XI function, which might explain the comparatively mild phenotype seen in our study. The identification of this candidate causative mutation thus widens the known phenotypic spectrum of COL11A2 mutations. We speculate that non-pathogenic COL11A2 variants might even contribute to the heritable variation in height.

  8. A COL11A2 mutation in Labrador retrievers with mild disproportionate dwarfism.

    Frischknecht, Mirjam; Niehof-Oellers, Helena; Jagannathan, Vidhya; Owczarek-Lipska, Marta; Drögemüller, Cord; Dietschi, Elisabeth; Dolf, Gaudenz; Tellhelm, Bernd; Lang, Johann; Tiira, Katriina; Lohi, Hannes; Leeb, Tosso

    2013-01-01

    We describe a mild form of disproportionate dwarfism in Labrador Retrievers, which is not associated with any obvious health problems such as secondary arthrosis. We designate this phenotype as skeletal dysplasia 2 (SD2). It is inherited as a monogenic autosomal recessive trait with incomplete penetrance primarily in working lines of the Labrador Retriever breed. Using 23 cases and 37 controls we mapped the causative mutation by genome-wide association and homozygosity mapping to a 4.44 Mb interval on chromosome 12. We re-sequenced the genome of one affected dog at 30x coverage and detected 92 non-synonymous variants in the critical interval. Only two of these variants, located in the lymphotoxin A (LTA) and collagen alpha-2(XI) chain gene (COL11A2), respectively, were perfectly associated with the trait. Previously described COL11A2 variants in humans or mice lead to skeletal dysplasias and/or deafness. The dog variant associated with disproportionate dwarfism, COL11A2:c.143G>C or p.R48P, probably has only a minor effect on collagen XI function, which might explain the comparatively mild phenotype seen in our study. The identification of this candidate causative mutation thus widens the known phenotypic spectrum of COL11A2 mutations. We speculate that non-pathogenic COL11A2 variants might even contribute to the heritable variation in height.

  9. Rare species contribute disproportionately to the functional structure of species assemblages.

    Leitão, Rafael P; Zuanon, Jansen; Villéger, Sébastien; Williams, Stephen E; Baraloto, Christopher; Fortunel, Claire; Mendonça, Fernando P; Mouillot, David

    2016-04-13

    There is broad consensus that the diversity of functional traits within species assemblages drives several ecological processes. It is also widely recognized that rare species are the first to become extinct following human-induced disturbances. Surprisingly, however, the functional importance of rare species is still poorly understood, particularly in tropical species-rich assemblages where the majority of species are rare, and the rate of species extinction can be high. Here, we investigated the consequences of local and regional extinctions on the functional structure of species assemblages. We used three extensive datasets (stream fish from the Brazilian Amazon, rainforest trees from French Guiana, and birds from the Australian Wet Tropics) and built an integrative measure of species rarity versus commonness, combining local abundance, geographical range, and habitat breadth. Using different scenarios of species loss, we found a disproportionate impact of rare species extinction for the three groups, with significant reductions in levels of functional richness, specialization, and originality of assemblages, which may severely undermine the integrity of ecological processes. The whole breadth of functional abilities within species assemblages, which is disproportionately supported by rare species, is certainly critical in maintaining ecosystems particularly under the ongoing rapid environmental transitions. © 2016 The Author(s).

  10. Complete genome sequence of Desulfocapsa sulfexigens, a marine deltaproteobacterium specialized in disproportionating inorganic sulfur compounds.

    Finster, Kai Waldemar; Kjeldsen, Kasper Urup; Kube, Michael; Reinhardt, Richard; Mussmann, Marc; Amann, Rudolf; Schreiber, Lars

    2013-04-15

    Desulfocapsa sulfexigens SB164P1 (DSM 10523) belongs to the deltaproteobacterial family Desulfobulbaceae and is one of two validly described members of its genus. This strain was selected for genome sequencing, because it is the first marine bacterium reported to thrive on the disproportionation of elemental sulfur, a process with a unresolved enzymatic pathway in which elemental sulfur serves both as electron donor and electron acceptor. Furthermore, in contrast to its phylogenetically closest relatives, which are dissimilatory sulfate-reducers, D. sulfexigens is unable to grow by sulfate reduction and appears metabolically specialized in growing by disproportionating elemental sulfur, sulfite or thiosulfate with CO2 as the sole carbon source. The genome of D. sulfexigens contains the set of genes that is required for nitrogen fixation. In an acetylene assay it could be shown that the strain reduces acetylene to ethylene, which is indicative for N-fixation. The circular chromosome of D. sulfexigens SB164P1 comprises 3,986,761 bp and harbors 3,551 protein-coding genes of which 78% have a predicted function based on auto-annotation. The chromosome furthermore encodes 46 tRNA genes and 3 rRNA operons.

  11. Hydrogen highway

    Anon

    2008-01-01

    The USA Administration would like to consider the US power generating industry as a basis ensuring both the full-scale production of hydrogen and the widespread use of the hydrogen related technological processes into the economy [ru

  12. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  13. Gas-phase hydrogenation of benzene on supported nickel catalyst

    Franco, H.A.; Phillips, M.J.

    1980-06-01

    The reaction of 22.66-280 Pa benzene with 72.39-122.79 Pa hydrogen on kieselguhr-supported nickel at 392.2/sup 0/-468.2/sup 0/K yielded only cyclohexane and was independent of 5.33-40 Pa cyclohexane added to the feed of the differential flow reactor. Best fit for the kinetic data was obtained with a rate equation developed by van Meerten and Coenen which assumed that all hydrogen addition steps have the same rate constant and are slow. An observed rate maximum at 458/sup 0/K may be the result of an increasing rate constant and decreasing cyclohexyl surface coverage as the temperature increases. Temperature-programed hydrogen desorption showed a series of desorption peaks at 358/sup 0/-600/sup 0/K, including one at 453/sup 0/K, which may be due to the hydrogen involved in the surface reaction.

  14. Universal scaling for biomolecule desorption induced by swift heavy ions

    Szenes, G.

    2005-01-01

    A thermal activation mechanism is proposed for the desorption of biomolecules. Good agreement is found with the experiments in a broad range of the electronic stopping power. The activation energies of desorption U are 0.33, 1.57 and 5.35 eV for positive, negative and neutral leucine molecules, respectively, and 2.05 eV for positive ergosterol molecules. The desorption of valine clusters is analyzed. The magnitude of the specific heat shows that the internal degrees of freedom are not excited up to the moment of desorption. The effect of irradiation temperature and of ion velocity on the desorption yield is discussed on the basis of the author's model. The scaling function derived in the model for the desorption of biomolecules is applied also to the sputtering of SiO 2 and U = 0.42 eV is obtained

  15. Thermal desorption and surface modification of He+ implanted into tungsten

    Fu Zhang; Yoshida, N.; Iwakiri, H.; Xu Zengyu

    2004-01-01

    Tungsten divertor plates in fusion reactors will be subject to helium bombardment. Helium retention and thermal desorption is a concerned issue in controlling helium ash. In the present study, fluence dependence of thermal desorption behavior of helium in tungsten was studied at different irradiation temperatures and ion energies. Results showed that helium desorption could start at ∼400 K with increasing fluence, while no noticeable peaks were detected at low fluence. Total helium desorption reached a saturation value at high fluence range, which was not sensitive to irradiation temperature or ion energy for the conditions evaluated. Surface modifications caused by either ion irradiation or thermal desorption were observed by SEM. The relationship of surface modifications and helium desorption behavior was discussed. Some special features of elevated irradiation temperature and lower ion energy were also indicated

  16. Hydriding properties of an Mg-Al-Ni-Nd hydrogen storage alloy

    Duarte, G.I.; Bustamante, L.A.C.; Miranda, P.E.V. de

    2007-01-01

    This work presents the development of an Mg-Al-Ni-Nd alloy for hydrogen storage purposes. The hydrogen storage properties of the alloy were analyzed using pressure-composition isotherms and hydrogen desorption kinetic curves at different temperatures. The characterization of the microstructures, before and after hydrogenation, was performed using X-ray diffraction, scanning electron microscopy and energy-dispersive spectrometry. Hydrogenation caused significant changes in the alloy microstructure. Two pressure plateaus were observed. The maximum hydrogen storage reversible capacity measured was 4 wt.% at 573 K

  17. Alcohol Advertising in Magazines and Underage Readership: Are Underage Youth Disproportionately Exposed?

    King, Charles; Siegel, Michael; Ross, Craig S; Jernigan, David H

    2017-10-01

    The question of whether underage youth are disproportionately exposed to alcohol advertising lies at the heart of the public health debate about whether restrictions on alcohol advertising are warranted. The aim of this study was to determine whether alcohol brands popular among underage (ages 12 to 20 years) drinkers ("underage brands") are more likely than others ("other brands") to advertise in magazines with high underage readerships. We analyze the advertising of 680 alcohol brands in 49 magazines between 2006 and 2011. Using a random effects probit model, we examine the relationship between a magazine's underage readership and the probability of an underage or other brand advertising in a magazine, controlling for young adult (ages 21 to 29 years) and total readerships, advertising costs and expenditures, and readership demographics. We find that underage brands are more likely than other brands to advertise in magazines with a higher percentage of underage readers. Holding all other variables constant at their sample means, the probability of an "other" brand advertising in a magazine remains essentially constant over the range of underage readership from 0.010 (95% confidence interval [CI], 0.007 to 0.013) at 5% to 0.012 (95% CI, 0.008 to 0.016) at 35%. In contrast, the probability of an underage brand advertising nearly quadruples, ranging from 0.025 (95% CI, 0.015 to 0.035) to 0.096 (95% CI, 0.057 to 0.135), where underage brands are 7.90 (95% CI, 3.89 to 11.90) times more likely than other brands to advertise. Alcohol brands popular among underage drinkers are more likely than other brands to advertise in magazines with high underage readerships, resulting in the disproportionate exposure of underage youth. Current voluntary advertising industry guidelines are not adequate to protect underage youth from high and disproportionate exposure to alcohol advertising in magazines. To limit advertising exposure among underage youth, policy makers may want to

  18. The effects of low fugacity hydrogen in duplex- and beta-annealed Ti-6Al-4V alloy

    Tal-Gutelmacher, E.; Eliezer, D.; Eylon, D.

    2004-01-01

    Due to its excellent combination of a high strength/weight ratio and good corrosion behavior, Ti-6Al-4V alloys are ranked among the most important advanced materials for a variety of aerospace, chemical engineering, biomaterials, marine and commercial applications. However, in many of these technological applications, this alloy is exposed to environments which can act as sources of hydrogen, and severe problems may arise based on its susceptibility to hydrogen embrittlement. Even small hydrogen concentrations might lead to failure. Consequently, a comprehensive knowledge of hydrogen-trapping interactions is necessary to better understand the trapping mechanisms, the types of the trap sites, the trapped hydrogen content, in order to determine the safe service conditions of this alloy in the aerospace industry. The objective of this paper is to investigate the role of microstructure on hydrogen absorption/desorption behavior in Ti-6Al-4V alloy, with specific emphasis on the nature of the interaction between microstructural traps and hydrogen atoms. The effect of low fugacity hydrogen on the microstructure is studied using X-ray diffraction (XRD), and electron microscopy (SEM and TEM), while the absorption and desorption characteristics are determined by means of a hydrogen determinator and thermal desorption spectroscopy (TDS), respectively. The role of microstructure on hydrogen absorption and desorption behavior is discussed in detail

  19. Microwave interaction with nonuniform hydrogen gas in carbon nanotubes

    Babaei, S.; Babaei, Sh.

    2009-01-01

    In this paper we study the reflection, absorption, and transmission of microwave from nonuniform hydrogen gas in carbon nanotubes, grown by iron-catalyzed high-pressure carbon monoxide disproportionate (HiPco) process. A discussion on the effect of various hydrogen gas parameters on the reflected power, absorbed power, and transmitted power is presented. The nonuniform hydrogen gas slab is modeled by a series of subslabs. The overall number density profile across the whole slab follows a parabolic function. The total reflected, absorbed, and transmitted powers are then deduced and their functional dependence on the number density, collision frequency, and angle of propagation is studied

  20. Mechanism of calcium oxide excitation by atom hydrogen

    Kharlamov, V.F.

    1991-01-01

    Heterogeneous recombination of hydrogen atoms on the surface of calcium oxide proceeds according to the Langmuir-Hinshelwood mechanism with participation of atoms in two different states, belonging to adsorption centres of the same type. CaO excitation is broughty about by vibration-electron transitions during associative desorption of H 2 molecules

  1. Hydrogen economy

    Pahwa, P.K.; Pahwa, Gulshan Kumar

    2013-10-01

    In the future, our energy systems will need to be renewable and sustainable, efficient and cost-effective, convenient and safe. Hydrogen has been proposed as the perfect fuel for this future energy system. The availability of a reliable and cost-effective supply, safe and efficient storage, and convenient end use of hydrogen will be essential for a transition to a hydrogen economy. Research is being conducted throughout the world for the development of safe, cost-effective hydrogen production, storage, and end-use technologies that support and foster this transition. This book discusses hydrogen economy vis-a-vis sustainable development. It examines the link between development and energy, prospects of sustainable development, significance of hydrogen energy economy, and provides an authoritative and up-to-date scientific account of hydrogen generation, storage, transportation, and safety.

  2. Trapping hydropyrolysates on silica and their subsequent desorption to facilitate rapid fingerprinting by GC-MS

    Meredith, W.; Russell, C.A.; Cooper, M.; Snape, C.E. [Nottingham Univ. (United Kingdom). Fuel and Energy Centre; Love, G.D. [Newcastle upon Tyne Univ. (United Kingdom). School of Civil Engineering and Geosciences; Fabbri, D. [Universita di Bologna, Ravenna (Italy). Lab. di Chimica Ambientale; Vane, C.H. [British Geological Society, Keyworth (United Kingdom)

    2004-01-01

    Analytical hydropyrolysis performed under high hydrogen gas pressure (>10 MPa) has been demonstrated to possess the unique ability to release high yields of biomarker hydrocarbons covalently bound within the non-hydrocarbon macromolecular fraction of crude oils and source rocks. This study describes the development of the experimental procedure for trapping the product oils (hydropyrolysates) on silica to facilitate more convenient recovery than conventional collection and to allow analysis by thermal desorption-GC-MS without any prior work-up. Conventionally, the trap has consisted of a stainless steel coil, cooled with dry ice from which the products are recovered in organic solvents. Replacing this with a system in which the hydropyrolysates are adsorbed on a small mass of silica greatly reduces the turn-around time between tests, and aids the recovery and separation of the products. This method has been developed using an oil shale and an oil asphaltene fraction, with the silica trap producing very similar biomarker profiles to that from the conventional trap. The quantitative recovery of hydrocarbons from a light crude oil desorbed from silica under hydropyrolysis conditions demonstrates no significant loss of the high molecular weight n-alkanes (>n-C{sub 10}) for both trapping methods. The use of liquid nitrogen as the trap coolant results in significantly improved recovery of the lower molecular mass constituents. The silica trapping method allows for the hydropyrolysates to be characterised by thermal desorption-GC-MS, which has been investigated both on- and off-line. The oils undergo relatively little cracking during desorption, with similar n-alkane and biomarker profiles being obtained as with normal work-up and GC-MS analysis. Thus, in terms of fingerprinting geomacromolecules, ''hypy-thermal desorption-GC-MS'' appears to have the potential to be developed as an attractive alternative to traditional py-GC-MS. (author)

  3. Non-thermal desorption from interstellar dust grains via exothermic surface reactions

    Garrod, R. T.; Wakelam, V.; Herbst, E.

    2007-06-01

    Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

  4. Desorption of trihalomethanes in gas liquid contactors

    Ramirez Quesada, Kenneth

    2000-01-01

    Updated studies show that gastric cancer is related with the existence of trihalomethanes (THMs) in the drinking water. The trihalomethanes are sub products from the degradation of humic acids and your reaction with chlorine and bromine used like decontaminates. The desorption process is used to eliminate the THMs with air in contact with the water. The experimental design was used in three contactors. The contactors selected were: the bubbling's column, the packed column and the shaken tank without screen. There were selected three variable: initial concentration of THMs, the residence time and the turbulence degree (measured with the Reynolds number). The concentrations were made with a gas chromatograph. The objective of this project is to do a comparison with the gas liquid contactors more used in the industrial level to determinate which ones are the best in the desorption process. The conclusion of the experimental design is that the tank is the equipment with the best capacity to eliminate THMs. Too it includes other techniques to eliminate THMs of the water and your treatment [es

  5. Disproportionately severe calcinosis cutis in an 88-year-old patient with CREST syndrome

    Buchowski, J.M.; Ahn, N.U.; Ahn, U.M. [Dept. of Orthopaedic Surgery, Johns Hopkins Univ. School of Medicine, Baltimore, MD (United States); McCarthy, E.F. [Dept. of Orthopaedic Surgery, Johns Hopkins Univ. School of Medicine, Baltimore, MD (United States); Dept. of Pathology, Johns Hopkins University School of Medicine, Baltimore, MD (United States); Mehta, M.B. [Clinical Associates, Good Samaritan Hospital, Baltimore, MD (United States)

    2001-08-01

    An 88-year-old woman with CREST syndrome (calcinosis, Raynaud's phenomenon, esophageal dysmotility, sclerodactyly, and telangiectasias) presented with hyperglycemia, intravascular depletion, and atrial fibrillation. The patient was found to have unusually severe calcinosis cutis in both legs extending from the knees to the ankles bilaterally, as well as Raynaud's phenomenon, sclerodactyly, and telangiectasias. The patient was normocalcemic and normophosphatemic. Although subcutaneous calcification is often seen with CREST syndrome, this case is unusual in that the area of involvement was much larger than previously described. Furthermore, the amount of calcinosis was disproportionately severe and was the major cause of symptoms and disability compared with the other components of the syndrome. (orig.)

  6. Charge disproportionation in RNiO3 at the metal-insulator transition

    Alonso, J.A.; Martinez-Lope, M.J.; Casais, M.T.; Garcia-Munoz, J.L.; Fernandez-Diaz, M.T.; Aranda, M.A.G.

    1999-01-01

    Complete text of publication follows. Neutron and synchrotron diffraction data provide the first observation of changes in the crystal symmetry at the metal-insulator (MI) transition in RNiO 3 perovskites [1]. At high temperatures, YNiO 3 is orthorhombic and metallic but below T MI = 582 K it changes to a monoclinic insulator. The monoclinic symmetry is due to a partial 2 Ni 3+ → Ni 3+δ + Ni 3-δ charge disproportionation associated to the MI transition. In the insulating state the presence of two NiO 6 octahedra is reported with, respectively, expanded (Ni1) and contracted (Ni2) Ni-O bonds, that alternated along the three directions of the crystal. Corroborating the charge disproportion, unequal moments are found at Ni1 and Ni2 octahedra in the low temperature monoclinic phase. (author) J.A. Alonso et al, Phys. Rev. Lett. in press

  7. How a mutation that slows aging can also disproportionately extend end-of-life decrepitude

    Podshivalova, Katie; Kerr, Rex A.; Kenyon, Cynthia

    2017-01-01

    Summary The goal of aging research is to extend healthy, active life. For decades, C. elegans daf-2 insulin/IGF-1 receptor mutants have served as a model for extended lifespan and youthfulness. However, a recent report suggested that their longevity is associated with an undesirable phenotype: a disproportionately long period of decrepitude at the end of life. In a human population, such an outcome would be a burden to society, bringing into question the relevance of daf-2 mutants as a model for life extension. However, here we report that, following an extended period of movement, daf-2 mutants survive longer in a decrepit state because of a beneficial trait: they are resistant to colonization of the digestive tract by dietary bacteria, a condition that leads to premature death in wild type and prevents their manifestation of decrepitude. If bacterial colonization is prevented, daf-2 mutants lead chronologically and proportionately healthier lives relative to wild type. PMID:28423308

  8. Energy and geometry of boron compounds. Halides BHHal2, BHal3 and their disproportionation

    Ionov, S.P.; Kuznetsov, N.T.

    1998-01-01

    Analysis of structural and thermodynamic parameters of boron halogen derivatives was conducted on the basis of structural-thermochemical (ST) model. Equilibrium interatomic B-H distances were specified for gaseous BHF 2 , BHCl 2 and BHBr 2 molecules. They were equal to 1.199±0.002, 1.175±0.003 and 1.79±0.01 A respectively. Formation heat was determined for BHI 2 : Δ f H 298 (BHI 2 (hg) = 72±5 kJ/mol. Qualitative analysis of thermodynamics of reactions of boron halide disproportionation was performed in the framework of ST-model: BHal 3 + 4BHal 3 . It was shown that halogen atoms weakened B-H-H bridges, halogens formed weak bridges in intermediate nonstable dimers

  9. Hydrogen storage by physisorption on porous materials

    Panella, B.

    2006-09-13

    A great challenge for commercializing hydrogen powered vehicles is on-board hydrogen storage using economic and secure systems. A possible solution is hydrogen storage in light-weight solid materials. Here three principle storage mechanisms can be distinguished: i) absorption of hydrogen in metals ii) formation of compounds with ionic character, like complex hydrides and iii) physisorption (or physical adsorption) of hydrogen molecules on porous materials. Physical adsorption exhibits several advantages over chemical hydrogen storage as for example the complete reversibility and the fast kinetics. Two classes of porous materials were investigated for physical hydrogen storage, i.e. different carbon nanostructures and crystalline metal-organic frameworks possessing extremely high specific surface area. Hydrogen adsorption isotherms were measured using a Sieverts' apparatus both at room temperature and at 77 K at pressures up to the saturation regime. Additionally, the adsorption sites of hydrogen in these porous materials were identified using thermal desorption spectroscopy extended to very low temperatures (down to 20 K). Furthermore, the adsorbed hydrogen phase was studied in various materials using Raman spectroscopy at different pressures and temperatures. The results show that the maximum hydrogen storage capacity of porous materials correlates linearly with the specific surface area and is independent of structure and composition. In addition the pore structure of the adsorbent plays an important role for hydrogen storage since the adsorption sites for H2 could be assigned to pores possessing different dimensions. Accordingly it was shown that small pores are necessary to reach high storage capacities already at low pressures. This new understanding may help to tailor and optimize new porous materials for hydrogen storage. (orig.)

  10. Hydrogen storage by physisorption on porous materials

    Panella, B

    2006-09-13

    A great challenge for commercializing hydrogen powered vehicles is on-board hydrogen storage using economic and secure systems. A possible solution is hydrogen storage in light-weight solid materials. Here three principle storage mechanisms can be distinguished: i) absorption of hydrogen in metals ii) formation of compounds with ionic character, like complex hydrides and iii) physisorption (or physical adsorption) of hydrogen molecules on porous materials. Physical adsorption exhibits several advantages over chemical hydrogen storage as for example the complete reversibility and the fast kinetics. Two classes of porous materials were investigated for physical hydrogen storage, i.e. different carbon nanostructures and crystalline metal-organic frameworks possessing extremely high specific surface area. Hydrogen adsorption isotherms were measured using a Sieverts' apparatus both at room temperature and at 77 K at pressures up to the saturation regime. Additionally, the adsorption sites of hydrogen in these porous materials were identified using thermal desorption spectroscopy extended to very low temperatures (down to 20 K). Furthermore, the adsorbed hydrogen phase was studied in various materials using Raman spectroscopy at different pressures and temperatures. The results show that the maximum hydrogen storage capacity of porous materials correlates linearly with the specific surface area and is independent of structure and composition. In addition the pore structure of the adsorbent plays an important role for hydrogen storage since the adsorption sites for H2 could be assigned to pores possessing different dimensions. Accordingly it was shown that small pores are necessary to reach high storage capacities already at low pressures. This new understanding may help to tailor and optimize new porous materials for hydrogen storage. (orig.)

  11. Heterozygous NPR2 Mutations Cause Disproportionate Short Stature, Similar to Léri-Weill Dyschondrosteosis.

    Hisado-Oliva, Alfonso; Garre-Vázquez, Ana I; Santaolalla-Caballero, Fabiola; Belinchón, Alberta; Barreda-Bonis, Ana C; Vasques, Gabriela A; Ramirez, Joaquin; Luzuriaga, Cristina; Carlone, Gianni; González-Casado, Isabel; Benito-Sanz, Sara; Jorge, Alexander A; Campos-Barros, Angel; Heath, Karen E

    2015-08-01

    SHOX mutations have been detected in approximately 70% of Léri-Weill dyschondrosteosis (LWD) and approximately 2.5% of idiopathic short stature (ISS) cases, suggesting the implication of other genes or loci. The recent identification of NPR2 mutations in ISS suggested that NPR2 mutations may also be involved in disproportionate short stature. The objective of the study was to investigate whether NPR2 mutations can account for a proportion of the cases referred for LWD and ISS in whom no SHOX mutation was detected. We undertook NPR2 mutation screening in 173 individuals referred for suspected LWD and 95 for ISS, with no known defect in SHOX or its enhancers. Intracellular localization and natriuretic peptide precursor C-dependent guanylate cyclase activity were determined for the identified NPR2 variants. Eight NPR2 variants were identified in nine individuals, seven referred for suspected LWD and two for ISS. Six were demonstrated to affect NPR-B cell trafficking and/or its ability to synthesize cyclic GMP (cGMP) under response to natriuretic peptide precursor C/brain natriuretic peptide stimulation. All pathogenic mutations were detected in the suspected LWD referral group (∼3%). Interestingly, one of these patients is currently being treated with recombinant human GH and in contrast to previous reports is showing a positive response to the treatment. NPR2 mutations account for approximately 3% of patients with disproportionate short stature and/or clinical or radiographic indicators of SHOX deficiency and in whom no SHOX defect has been identified. However, no patient has yet presented with Madelung deformity. Thus, NPR2 should be screened in the SHOX-negative LWD referrals.

  12. Skeletal dysplasia with craniofacial deformity and disproportionate dwarfism in hair sheep of northeastern Brazil.

    Dantas, F P M; Medeiros, G X; Figueiredo, A P M; Thompson, K; Riet-Correa, F

    2014-01-01

    This paper reports a newly described form of skeletal dysplasia affecting Brazilian hair sheep of the Cabugi breed. This breed is characterized by having a short head and in some cases the animals are smaller and more compact than sheep of similar breeds. Lambs born with craniofacial abnormalities and dwarfism that die at 2-6 months of age are frequent in this breed. In a flock of 68 ewes and three rams of the Cabugi breed, 134 lambs were born over a 4-year period. Of these, 14 (10.4%) had marked cranial abnormalities and dwarfism and died or were humanely destroyed, 43 (32%) had a normal face and 77 (57.5%) had the short face characteristic of the breed. Dwarf lambs were much smaller than normal, with short legs, a domed head with retruded muzzle and protruded mandible, sternal deformities and exophthalmic eyes situated more laterally in the face than normal. Microscopical examination of long bones of the limbs, bones of the base of the skull and vertebrae showed no lesions. Bones from four affected lambs and one control lamb were macerated for morphometric examination. Although the length of the spinal cord was similar, there was disproportionate shortening of the appendicular bones, particularly the distal segments. Thus the disease was defined as a skeletal dysplasia characterized by craniofacial deformity and disproportionate dwarfism. It is suggested that the disease is inherited as an incomplete dominant trait. The shortened face, which is a feature of the Cabugi breed, may represent the heterozygous state and the more severe, often lethal, dwarfism may occur in homozygotes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

    Bari, Sara E; Amorebieta, Valentín T; Gutiérrez, María M; Olabe, José A; Doctorovich, Fabio

    2010-01-01

    The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

  14. Performance of rare earth modified faujasites in the process of toluene disproportionation

    Azzouz, A.; Fourar, M.; Berrak, A.

    1984-06-01

    The purpose of the present paper is the study of the performances of some catalysts based on y-type faujasite exchanged with La (3+) and Ce (3+) cations in the process of toluene disproportionation to benzene and xylenes. In the first stage the crystallographic study by the X-rays diffraction method shows that the cation exchange causes 311 plane displacements in the zeolite structure, accompanied by a decrease of diffraction limit intensity. Further the faujasite pretreatment with NH4 (4+) ions plays some role in the protection of the crystallinity. Moreover the cation exchange seems to take an optimum value around 73% for which the toluene conversion is maximum. This phenomenon is probably due to a decrease of the internal free volume for a pronounced cation exchange. The best performances are obtained by the zeolite that has undergone a slow and programmed thermal activation after cation exchange. This is probably due to the slowness of ion rearrangement phenomena, and of the catalytic surface restructuration. In the second stage the realization of toluene disproportionation process shows that the cation exchange with such elements confers to the faujasite an appreciable catalytic activity in the temperature range of 350-500 degC. The catalysts obtained permit about 20-60% toluene conversions. The catalytic activity is slightly higher in La-modified samples, whereas those containing Ce (3+) present relatively a better selectivity to the main process. Nevertheless, both types of catalysts show approximately a similar behaviour, favourizing the p-xylene formation. The proportion of the latter exceeds that of thermodynamic equilibrium at temperatures less than 430 degC. The temperature increase affects this selectivity. This is probably due to dehydration phenomenon which are frequent around this value

  15. Sulfite-oxido-reductase is involved in the oxidation of sulfite in Desulfocapsa sulfoexigens during disproportionation of thiosulfate and elemental sulfur.

    Frederiksen, Trine-Maria; Finster, Kai

    2003-06-01

    The enzymatic pathways of elemental sulfur and thiosulfate disproportionation were investigated using cell-free extract of Desulfocapsa sulfoexigens. Sulfite was observed to be an intermediate in the metabolism of both compounds. Two distinct pathways for the oxidation of sulfite have been identified. One pathway involves APS reductase and ATP sulfurylase and can be described as the reversion of the initial steps of the dissimilatory sulfate reduction pathway. The second pathway is the direct oxidation of sulfite to sulfate by sulfite oxidoreductase. This enzyme has not been reported from sulfate reducers before. Thiosulfate reductase, which cleaves thiosulfate into sulfite and sulfide, was only present in cell-free extract from thiosulfate disproportionating cultures. We propose that this enzyme catalyzes the first step in thiosulfate disproportionation. The initial step in sulfur disproportionation was not identified. Dissimilatory sulfite reductase was present in sulfur and thiosulfate disproportionating cultures. The metabolic function of this enzyme in relation to elemental sulfur or thiosulfate disproportionation was not identified. The presence of the uncouplers HQNO and CCCP in growing cultures had negative effects on both thiosulfate and sulfur disproportionation. CCCP totally inhibited sulfur disproportionation and reduced thiosulfate disproportionation by 80% compared to an unamended control. HQNO reduced thiosulfate disproportionation by 80% and sulfur disproportionation by 90%.

  16. Hydrogen safety

    Frazier, W.R.

    1991-01-01

    The NASA experience with hydrogen began in the 1950s when the National Advisory Committee on Aeronautics (NACA) research on rocket fuels was inherited by the newly formed National Aeronautics and Space Administration (NASA). Initial emphasis on the use of hydrogen as a fuel for high-altitude probes, satellites, and aircraft limited the available data on hydrogen hazards to small quantities of hydrogen. NASA began to use hydrogen as the principal liquid propellant for launch vehicles and quickly determined the need for hydrogen safety documentation to support design and operational requirements. The resulting NASA approach to hydrogen safety requires a joint effort by design and safety engineering to address hydrogen hazards and develop procedures for safe operation of equipment and facilities. NASA also determined the need for rigorous training and certification programs for personnel involved with hydrogen use. NASA's current use of hydrogen is mainly for large heavy-lift vehicle propulsion, which necessitates storage of large quantities for fueling space shots and for testing. Future use will involve new applications such as thermal imaging

  17. Hydrogen absorption study of Ti-based alloys performed by melt-spinning

    Ribeiro, R.M.; Lemus, L.F.; Santos, D.S. dos, E-mail: rafaella@metalmat.ufrj.br [Coordenacao dos Programas de Pos-Graduacao em Engenharia (PEMM/COPPEP/UFRJ), Rio de Janeiro, RJ (Brazil). Programa de Engenharia Metalurgica e de Materiais

    2013-11-01

    The hydrogen absorption and desorption of Ti{sub 53}Zr{sub 27}Ni{sub 20} icosahedral quasicrystal (ICQ) and Ti{sub 50}Ni{sub 50} shape memory alloy (SMA) melt-spun ribbons was studied. Samples were exposed to hydrogen gas at 623 K and 4 MPa for 1000 minutes. The total capacity of hydrogen obtained for Ti{sub 53}Zr{sub 27}Ni{sub 20} and Ti{sub 50}Ni{sub 50} was 3.2 and 2.4 wt. % respectively. The Thermal Desorption Spectrometry (TDS) of the hydrogenated alloys shows that both alloys start to desorb hydrogen around 750 K. X-ray diffraction (XRD) patterns, performed after hydrogenation, indicate a complete amorphization of the Ti{sub 53}Zr{sub 27}Ni{sub 20} i-phase alloy, while the Ti{sub 50}Ni{sub 50} alloy remained crystalline after hydride formation. (author)

  18. Hydrogen Embrittlement

    Woods, Stephen; Lee, Jonathan A.

    2016-01-01

    Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of

  19. Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

    Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

    2017-06-01

    Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg 2 NiH 4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg 2 NiH 4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol -1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Recent progress of hydrogen isotope behavior studies for neutron or heavy ion damaged W

    Oya, Yasuhisa, E-mail: syoya@ipc.shizuoka.ac.jp [Shizuoka University, 836 Ohya, Suruga-ku Shizuoka 422-8529 (Japan); Hatano, Yuji [University of Toyama, 3190 Gofuku, Toyama 939-8555 (Japan); Shimada, Masashi [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Buchenauer, Dean; Kolasinski, Robert [Sandia National Laboratories, Livermore, CA 94551 (United States); Merrill, Brad [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Kondo, Sosuke; Hinoki, Tatsuya [Kyoto University, Gokasho, Uji 611-0011 (Japan); Alimov, Vladimir Kh. [University of Toyama, 3190 Gofuku, Toyama 939-8555 (Japan)

    2016-12-15

    Highlights: • This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. • Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. • The distribution of defects throughout the sample also changes the shape of TDS spectrum. • Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed. - Abstract: This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. In particular, the desorption temperature shifts higher as the defect concentration increases. In addition, the distribution of defects throughout the sample also changes the shape of TDS spectrum. Even if low energy traps were distributed in the bulk region, the D diffusion toward the surface requires additional time for trapping/detrapping during surface-to-bulk transport, contributing to a shift of desorption peaks toward higher temperatures. It can be said that both of distribution of damage (e.g. hydrogen isotope trapping sites) and their stabilities would have a large impact on desorption. In addition, transmutation effects should be also considered for an actual fusion environment. Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed.

  1. Recent progress of hydrogen isotope behavior studies for neutron or heavy ion damaged W

    Oya, Yasuhisa; Hatano, Yuji; Shimada, Masashi; Buchenauer, Dean; Kolasinski, Robert; Merrill, Brad; Kondo, Sosuke; Hinoki, Tatsuya; Alimov, Vladimir Kh.

    2016-01-01

    Highlights: • This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. • Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. • The distribution of defects throughout the sample also changes the shape of TDS spectrum. • Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed. - Abstract: This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. In particular, the desorption temperature shifts higher as the defect concentration increases. In addition, the distribution of defects throughout the sample also changes the shape of TDS spectrum. Even if low energy traps were distributed in the bulk region, the D diffusion toward the surface requires additional time for trapping/detrapping during surface-to-bulk transport, contributing to a shift of desorption peaks toward higher temperatures. It can be said that both of distribution of damage (e.g. hydrogen isotope trapping sites) and their stabilities would have a large impact on desorption. In addition, transmutation effects should be also considered for an actual fusion environment. Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed.

  2. Hydrogen storage thermodynamics and kinetics of LaMg11Ni + x wt.% Ni (x = 100, 200) alloys synthesized by mechanical milling

    Zhang, Yanghuan; Jia, Zhichao; Central Iron and Steel Research Institute, Beijing; Yuan, Zeming; Qi, Yan; Zhao, Dongliang; Hou, Zhonghui

    2016-01-01

    LaMg 11 Ni + x wt.% Ni (x = 100, 200) composite hydrogen storage alloys with a nanocrystalline/amorphous structure were synthesized using ball milling technology. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were investigated systematically. The hydrogen desorption properties were assessed using a Sieverts apparatus and differential scanning calorimetry. The thermodynamic parameters for the hydrogen absorption and desorption were calculated using the Van't Hoff equation. The hydrogen desorption activation energies of the hydrogenated alloys were also estimated by Arrhenius and Kissinger methods. Results indicate that the amount of Ni added has no effect on the thermodynamics of the alloys, but it significantly improves their absorption and desorption kinetics. Furthermore, the milling time has a great influence on the hydrogen storage properties. To be specific, the hydrogen absorption capacities reach the maximum values with the variation of milling time, and the hydrogen desorption activation energy obviously decreases with increasing milling time.

  3. Modeling Organic Contaminant Desorption from Municipal Solid Waste Components

    Knappe, D. R.; Wu, B.; Barlaz, M. A.

    2002-12-01

    Approximately 25% of the sites on the National Priority List (NPL) of Superfund are municipal landfills that accepted hazardous waste. Unlined landfills typically result in groundwater contamination, and priority pollutants such as alkylbenzenes are often present. To select cost-effective risk management alternatives, better information on factors controlling the fate of hydrophobic organic contaminants (HOCs) in landfills is required. The objectives of this study were (1) to investigate the effects of HOC aging time, anaerobic sorbent decomposition, and leachate composition on HOC desorption rates, and (2) to simulate HOC desorption rates from polymers and biopolymer composites with suitable diffusion models. Experiments were conducted with individual components of municipal solid waste (MSW) including polyvinyl chloride (PVC), high-density polyethylene (HDPE), newsprint, office paper, and model food and yard waste (rabbit food). Each of the biopolymer composites (office paper, newsprint, rabbit food) was tested in both fresh and anaerobically decomposed form. To determine the effects of aging on alkylbenzene desorption rates, batch desorption tests were performed after sorbents were exposed to toluene for 30 and 250 days in flame-sealed ampules. Desorption tests showed that alkylbenzene desorption rates varied greatly among MSW components (PVC slowest, fresh rabbit food and newsprint fastest). Furthermore, desorption rates decreased as aging time increased. A single-parameter polymer diffusion model successfully described PVC and HDPE desorption data, but it failed to simulate desorption rate data for biopolymer composites. For biopolymer composites, a three-parameter biphasic polymer diffusion model was employed, which successfully simulated both the initial rapid and the subsequent slow desorption of toluene. Toluene desorption rates from MSW mixtures were predicted for typical MSW compositions in the years 1960 and 1997. For the older MSW mixture, which had a

  4. Mechanism of NH{sub 3} desorption during the reaction of H{sub 2} with nitrogen containing carbonaceous materials

    Juan F. Espinal; Thanh N. Truong; Fanor Mondragon [University of Antioquia, Medellin (Colombia). Institute of Chemistry

    2005-07-01

    The continued increase in demand for natural gas has stimulated the interest in coal conversion to methane as synthetic natural gas by hydropyrolysis of coal (pyrolysis in a H{sub 2} atmosphere). Because the produced raw gas contains considerable amounts of gaseous N-containing products that have to be removed before delivering to final users, the information on distribution of coal-N is important for designing purification processes. It has been reported in the literature that NH{sub 3} is the main nitrogen containing gas that is released during the hydropyrolysis process. Other gases such as HCN and N{sub 2} are also released but in a much smaller amount. To the best of our knowledge, the mechanism for NH{sub 3} desorption during hydrogen reaction with carbonaceous materials has not been studied. We carried out a molecular modeling study using Density Functional Theory in order to get an insight of the mechanism and thermodynamics for NH{sub 3} evolution using pyridinic nitrogen as a model of N-containing carbonaceous material. We propose a mechanism that involves consecutive hydrogenation steps that lead to C-N bond breakage and NH{sub 3} desorption to the gas phase. It was found that the first hydrogenation reaction is highly exothermic. However, further hydrogenations are endothermic. Several pathways for NH{sub 3} evolution were proposed and most of them show high exothermicity. 17 refs., 2 figs.

  5. Hydrogen millennium

    Bose, T.K.; Benard, P.

    2000-05-01

    The 10th Canadian Hydrogen Conference was held at the Hilton Hotel in Quebec City from May 28 to May 31, 2000. The topics discussed included current drivers for the hydrogen economy, the international response to these drivers, new initiatives, sustainable as well as biological and hydrocarbon-derived production of hydrogen, defense applications of fuel cells, hydrogen storage on metal hydrides and carbon nanostructures, stationary power and remote application, micro-fuel cells and portable applications, marketing aspects, fuel cell modeling, materials, safety, fuel cell vehicles and residential applications. (author)

  6. Copper desorption from Gelidium algal biomass.

    Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

    2007-04-01

    Desorption of divalent copper from marine algae Gelidium sesquipedale, an algal waste (from agar extraction industry) and a composite material (the algal waste immobilized in polyacrylonitrile) was studied in a batch system. Copper ions were first adsorbed until saturation and then desorbed by HNO(3) and Na(2)EDTA solutions. Elution efficiency using HNO(3) increases as pH decreases. At pH=1, for a solid to liquid ratio S/L=4gl(-1), elution efficiency was 97%, 95% and 88%, the stoichiometric coefficient for the ionic exchange, 0.70+/-0.02, 0.73+/-0.05 and 0.76+/-0.06 and the selectivity coefficient, 0.93+/-0.07, 1.0+/-0.3 and 1.1+/-0.3, respectively, for algae Gelidium, algal waste and composite material. Complexation of copper ions by EDTA occurs in a molar proportion of 1:1 and the elution efficiency increases with EDTA concentration. For concentrations of 1.4, 0.88 and 0.57 mmoll(-1), the elution efficiency for S/L=4gl(-1), was 91%, 86% and 78%, respectively, for algae Gelidium, algal waste and composite material. The S/L ratio, in the range 1-20gl(-1), has little influence on copper recovery by using 0.1M HNO(3). Desorption kinetics was very fast for all biosorbents. Kinetic data using HNO(3) as eluant were well described by the mass transfer model, considering the average metal concentration in the solid phase and the equilibrium relationship given by the mass action law. The homogeneous diffusion coefficient varied between 1.0 x 10(-7)cm(2)s(-1) for algae Gelidium and 3.0 x 10(-7)cm(2)s(-1) for the composite material.

  7. Interaction of hydrogen and oxygen with continuous or granular films of palladium

    Mikhalenko, I.I.; Prokopov, A.M.; Yagodovskii, V.D.

    1986-03-01

    The authors use desorption and conductometric methods in establishing the existence of three species of adsorbed hydrogen on continuous Pd films and two species on Pd films with a granular structure. Preoxidation of the surface of the continuous films does not affect the rate or kinetic order of hydrogen sorption; oxidation/reduction treatment changes these parameters, but the magnitude of Edes of hydrogen remains unchanged.

  8. Structural studies of charge disproportionation and magnetic order in CaFeO3

    Woodward, P.M.; Cox, D.E.; Moshopoulou, E.; Sleight, A.W.; Morimoto, S.

    2000-01-01

    The crystal and magnetic structures of CaFeO 3 have been determined at 300 and 15 K using synchrotron x-ray and neutron powder-diffraction techniques. At 300 K, CaFeO 3 adopts the GdFeO 3 structure, space group Pbnm with unit-cell dimensions a=5.326 30(4), b=5.352 70(4), and c=7.539 86(6) A. This structure is distorted from the ideal perovskite structure by tilting of the FeO 6 octahedra about [110] and [001]. The average Fe-O distance is 1.922(2) A, and the Fe-O-Fe angles are 158.4(2) deg. and 158.1(1) deg. . At 15 K the crystal structure belongs to space group P2 1 /n with a=5.311 82(3), b=5.347 75(4), c=7.520 58(5) A and β=90.065(1) deg. , and contains two distinct Fe sites. The average Fe-O bond length is 1.872(6) A about the one iron site, and 1.974(6) A about the second site, with bond valence sums of 4.58 and 3.48, respectively. This provides quantitative evidence for charge disproportionation, 2Fe 4+ →Fe 3+ +Fe 5+ , at low temperature. The temperature evolution of the lattice parameters indicates a second- (or higher-) order phase transition from the orthorhombic charge-delocalized state to the monoclinic charge-disproportionated state, beginning just below room temperature. The magnetic structure at 15 K is incommensurate, having a modulation vector [δ,0,δ] with δ ∼0.322, corresponding to one of the directions in the pseudocubic cell. A reasonable fit to the magnetic intensities is obtained with the recently proposed screw spiral structure [S. Kawasaki et al., J. Phys. Soc. Jpn. 67, 1529 (1998)], with Fe moments of 3.5 and 2.5μ B , respectively. However, a comparable fit is given by a sinusoidal amplitude-modulated model in which the Fe moments are directed along [010], which leaves open the possibility that the true magnetic structure may be intermediate between the spiral and sinusoidal models (a fan structure)

  9. Interaction of hydrogen with palladium clusters deposited on graphene

    Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J. [Departamento de Física Teórica, Atómica y Optica, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-12-31

    Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H{sub 2} on Pd{sub 6} anchored on a graphene vacancy has been studied in detail.

  10. Interaction of hydrogen with palladium clusters deposited on graphene

    Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J.

    2015-12-01

    Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H2 on Pd6 anchored on a graphene vacancy has been studied in detail.

  11. Hydrogenation of carbon monoxide over supported palladium catalysts

    Fujimoto, K.; Hashimoto, H.; Kunugi, T.

    1978-03-01

    An alumina-supported 2% palladium catalyst had higher activity for carbon monoxide hydrogenation than a silica-supported 2% palladium catalyst, at 250/sup 0/-400/sup 0/C and 1 atm. The addition of lanthanum oxide or thorium oxide, but not of potassium oxide, to the silica-supported catalyst increased the conversion at 350/sup 0/C from 1.1% to 81.0% with a selectivity of 56.1% for methane, 1.4% for C/sub 2/ compounds, 0.1% for C/sub 3/ compounds, and 42.5% for carbon dioxide. Temperature-programed desorption of carbon monoxide in a hydrogen stream showed that of two desorption peaks observed for carbon monoxide, the one at higher temperature corresponded to the carbon monoxide species which hydrogenates to methane and that the area of this peak increased with increasing thorium content of the catalyst. Graphs, tables, and 12 references.

  12. Nanocrystalline electrodeposited Ni-Mo-C cathodes for hydrogen production

    Hashimoto, K.; Sasaki, T.; Meguro, S.; Asami, K.

    2004-01-01

    Tailoring active nickel alloy cathodes for hydrogen evolution in a hot concentrated hydroxide solution was attempted by electrodeposition. The carbon addition to Ni-Mo alloys decreased the nanocrystalline grain size and remarkably enhanced the activity for hydrogen evolution, changing the mechanism of hydrogen evolution. The Tafel slope of hydrogen evolution was about 35 mV per decade. This suggested that the rate-determining step is desorption of adsorbed hydrogen atoms by recombination. As was distinct from the binary Ni-Mo alloys, after open circuit immersion, the overpotential, that is, the activity of nanocrystalline Ni-Mo-C alloys for hydrogen evolution was not changed, indicating the sufficient durability in the practical electrolysis

  13. Microporous Metal Organic Materials for Hydrogen Storage

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  14. Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

    Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

    2015-11-28

    We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

  15. Hydrogen exchange

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  16. Charge transfer processes during ion scattering and stimulated desorption of secondary ions from gas-condensed dielectric surfaces

    Souda, R

    2002-01-01

    The ion emission mechanism from weakly-interacting solid surfaces has been investigated. The H sup + ion captures a valence electron via transient chemisorption, so that the ion neutralization probability is related to the nature of bonding of adsorbates. The H sup + ion is scattered from physisorbed Ar at any coverage whereas the H sup + yield from solid H sub 2 O decays considerably due to covalency in the hydrogen bond. In electron- and ion-stimulated desorption, the ion ejection probability is correlated intimately with the physisorption/chemisorption of parent atoms or molecules. The emission of F sup + ions is rather exceptional because they arise from the screened F 2s core-hole state followed by the ionization via the intra-atomic Auger decay after bond breakage. In electron-stimulated desorption of H sub 2 O, hydrated protons are emitted effectively from nanoclusters formed on a solid Ar substrate due to Coulomb repulsion between confined valence holes.

  17. Comparative Study Between Ethylbenzene Disproportionation Reaction and its Ethylation Reaction with Ethanol over ZSM-5

    Tukur, N. M.

    2009-06-23

    Ethylation of ethylbenzene with ethanol has been studied over ZSM-5 catalyst in a riser simulator that mimics the operation of a fluidized-bed reactor. The feed molar ratio of ethylbenzene:ethanol is 1:1. The study was carried out at 350, 400, 450, and 500°C for reaction times of 3, 5, 7, 10, 13, and 15 s. Comparisons are made between the results of the ethylbenzene ethylation reaction with that of ethylbenzene disproportionation reaction earlier reported. The effect of reaction conditions on ethylbenzene reactivity, p-diethylbenzene selectivity, total diethylbenzene (DEB) isomers selectivity, p-DEB-to-m-DEB ratio, benzene-to-DEB molar ratio, and benzene selectivity, are reported. Benzene selectivity is about 10 times more in the EB disproportion reaction as compared to its ethylation reaction with ethanol at 350°C. In addition, the results showed a p-DEB/m-DEB ratio for the EB ethylation reaction varying between 1.2-1.7, which is greater than the equilibrium values. Increase in temperature shifts the alkylation/dealkylation equilibrium towards dealkylation, thereby decreasing conversion and selectivity to DEB. © Springer Science+Business Media, LLC 2009.

  18. Morphometrics and behavior of a wild Asian elephant exhibiting disproportionate dwarfism.

    de Silva, Shermin; Weerathunga, U Sameera; Pushpakumara, Tennekoon V

    2014-12-19

    Dwarfism is a condition characterized by shorter stature, at times accompanied by differential skeletal growth proportions relative to the species-typical physical conformation. Causes vary and are well-documented in humans as well as certain mammalian species in captive or laboratory conditions, but rarely observed in the wild. We report on a single case of apparent dwarfism in a free-ranging adult male Asian elephant in Sri Lanka, comparing physical dimensions to those of other males in the population as well as in previous literature. The subject M459 was found to have a shoulder height of approximately 195 cm, is shorter than the average height of typical mature males, with a body length of 218 cm. This ratio of body length to height deviates from what is typically observed, which is approximately 1:1, but was similar to the attributes of a dwarf elephant in captivity documented in 1955. We report on behavior including the surprising observation that M459 appears to have a competitive advantage in intrasexual contests. We discuss how this phenotype compares to cases of dwarfism in other non-human animals. M459 exemplifies a rare occurrence of disproportionate dwarfism in a free-ranging wild mammal that has survived to reproductive maturity and appears otherwise healthy.

  19. Indirect medical education and disproportionate share adjustments to Medicare inpatient payment rates.

    Nguyen, Nguyen Xuan; Sheingold, Steven H

    2011-11-04

    The indirect medical education (IME) and disproportionate share hospital (DSH) adjustments to Medicare's prospective payment rates for inpatient services are generally intended to compensate hospitals for patient care costs related to teaching activities and care of low income populations. These adjustments were originally established based on the statistical relationships between IME and DSH and hospital costs. Due to a variety of policy considerations, the legislated levels of these adjustments may have deviated over time from these "empirically justified levels," or simply, "empirical levels." In this paper, we estimate the empirical levels of IME and DSH using 2006 hospital data and 2009 Medicare final payment rules. Our analyses suggest that the empirical level for IME would be much smaller than under current law-about one-third to one-half. Our analyses also support the DSH adjustment prescribed by the Affordable Care Act of 2010 (ACA)--about one-quarter of the pre-ACA level. For IME, the estimates imply an increase in costs of 1.88% for each 10% increase in teaching intensity. For DSH, the estimates imply that costs would rise by 0.52% for each 10% increase in the low-income patient share for large urban hospitals. Public Domain.

  20. Disproportionate cardiac hypertrophy during early postnatal development in infants born preterm.

    Aye, Christina Y L; Lewandowski, Adam J; Lamata, Pablo; Upton, Ross; Davis, Esther; Ohuma, Eric O; Kenworthy, Yvonne; Boardman, Henry; Wopperer, Samuel; Packham, Alice; Adwani, Satish; McCormick, Kenny; Papageorghiou, Aris T; Leeson, Paul

    2017-07-01

    BackgroundAdults born very preterm have increased cardiac mass and reduced function. We investigated whether a hypertrophic phenomenon occurs in later preterm infants and when this occurs during early development.MethodsCardiac ultrasound was performed on 392 infants (33% preterm at mean gestation 34±2 weeks). Scans were performed during fetal development in 137, at birth and 3 months of postnatal age in 200, and during both fetal and postnatal development in 55. Cardiac morphology and function was quantified and computational models created to identify geometric changes.ResultsAt birth, preterm offspring had reduced cardiac mass and volume relative to body size with a more globular heart. By 3 months, ventricular shape had normalized but both left and right ventricular mass relative to body size were significantly higher than expected for postmenstrual age (left 57.8±41.9 vs. 27.3±29.4%, P<0.001; right 39.3±38.1 vs. 16.6±40.8, P=0.002). Greater changes were associated with lower gestational age at birth (left P<0.001; right P=0.001).ConclusionPreterm offspring, including those born in late gestation, have a disproportionate increase in ventricular mass from birth up to 3 months of postnatal age. These differences were not present before birth. Early postnatal development may provide a window for interventions relevant to long-term cardiovascular health.

  1. How a Mutation that Slows Aging Can Also Disproportionately Extend End-of-Life Decrepitude

    Katie Podshivalova

    2017-04-01

    Full Text Available Summary: The goal of aging research is to extend healthy, active life. For decades, C. elegans daf-2 insulin/insulin-like growth factor 1 (IGF-1 receptor mutants have served as a model for extended lifespan and youthfulness. However, a recent report suggested that their longevity is associated with an undesirable phenotype: a disproportionately long period of decrepitude at the end of life. In the human population, such an outcome would be a burden to society, bringing into question the relevance of daf-2 mutants as a model for life extension. However, here we report that, following an extended period of movement, daf-2 mutants survive longer in a decrepit state because of a beneficial trait: they are resistant to colonization of the digestive tract by dietary bacteria, a condition that leads to premature death in the wild-type and prevents their manifestation of decrepitude. If bacterial colonization is prevented, then daf-2 mutants lead both chronologically and proportionately healthier lives relative to the wild-type. : Podshivalova et al. show that long-lived C. elegans insulin/IGF-1 receptor mutants remain active longer but then resist bacterially induced mortality, allowing them to survive into a state of end-of-life decrepitude. Thus, changes that slow aging and also prevent an age-associated catastrophe can extend both the youthful and infirm periods of life. Keywords: aging, lifespan, healthspan, daf-2, mortality, IGF-1, pathogenesis

  2. Crystal dimension of ZSM-5 influences on para selective disproportionation of ethylbenzene.

    Hariharan, Srinivasan; Palanichamy, Muthaiahpillai

    2014-03-01

    Crystal size and crystal dimensions are vital role in shape selective feature. Para selective disproportionation of EthylBenzene (Dip-EB) was investigated over ZSM-5 synthesized in acidic medium. The catalysts were prepared by hydrothermal process with various Si/Al ratios (50, 75 and 100) using fluoride ion precursor. This fluoride ion precursor dissolves the ZSM-5 nutrients below it neutral pH between 4 and 6. The synthesized material was subjected into various physico chemical characterizations such as XRD, SEM, TGA and BET analyses. The XRD patterns showed high crystalline nature and their resulting SEM images were also indicate thin prismatic crystals of large dimension compared with alkaline medium synthesized one. The BET results earned good textural property. Catalytic activity of vapor phase Dip-EB was carried out between 523 and 673 K. As their result, diethylbenzene (DEB) isomers were obtained, but para selective Diethylbenzene (p-DEB) was observed higher than others. The high selectivity towards p-DEB was due to large crystal dimension of ZSM-5 catalysts synthesized in fluoride medium. Hence it is good commercial application for petrochemical feed stock production.

  3. Familial chronic lymphocytic leukemia in Israel: A disproportionate distribution among Ashkenazi Jews.

    Zada, Mor; Lerner, Daniele; Piltz, Yuval; Perry, Chava; Avivi, Irit; Herishanu, Yair

    2017-07-01

    Relatives of patients with chronic lymphocytic leukemia (CLL) are at increased risk of developing CLL. Familial CLL is defined as more than one case of CLL among blood relatives, a phenomenon reported in approximately 5%-10% of all CLL patients. Given the known predisposition of CLL among Ashkenazi Jews, we studied the features of familial CLL in an Israeli population. This is a retrospective study, in which we reviewed the demographics, clinical characteristics, and outcomes of a total of 332 patients with CLL/small lymphocytic lymphoma. Familial CLL was recorded in 41 cases (12.3%) of the patients. The age at diagnosis was younger in patients with familial CLL (by almost 3.5 years). Familial CLL was strongly associated with Ashkenazi Jewish origin. Patients with familial CLL more commonly presented with higher hemoglobin and lower serum β-2-microglobulin levels. No significant differences were detected between sporadic and familial CLL in disease stage, time to treatment, second cancers, or overall survival. Familial cases of CLL in an Israeli population show a disproportionate ethnic distribution toward Jews of Ashkenazi origin. The clinical characteristics and the overall outcome are not substantially different from sporadic cases. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  4. Hydrogen storage in Ti-Mn-(FeV) BCC alloys

    Santos, S.F.; Huot, J.

    2009-01-01

    Recently, the replacement of vanadium by the less expensive (FeV) commercial alloy has been investigated in Ti-Cr-V BCC solid solutions and promising results were reported. In the present work, this approach of using (FeV) alloys is adopted to synthesize alloys of the Ti-Mn-V system. Compared to the V-containing alloys, the alloys containing (FeV) have a smaller hydrogen storage capacity but a larger reversible hydrogen storage capacity, which is caused by the increase of the plateau pressure of desorption. Correlations between the structure and the hydrogen storage properties of the alloys are also discussed.

  5. Hydrogenated amorphous carbon next deposit after heat treatment

    Salancon, E.; Durbeck, T.; Schwarz-Selinger, T.; Jacob, W.

    2006-01-01

    One of the main safety problems in the ITER tokamak project is the tritium adsorption in the reactor walls and in particular the deposits which appear after the plasma discharge. These deposits are amorphous hydrogenated carbon films, type polymer (soft a-C:H). The heating of these deposits with a pulse laser is a proposed solution for the tritium desorption. Meanwhile, Gibson and al show that in experimental conditions, products are deposed on the walls before entering the mass spectrometer. The authors present thermo-desorption spectra of different amorphous carbon films. (A.L.B.)

  6. Catalyst support effects on hydrogen spillover

    Karim, Waiz; Spreafico, Clelia; Kleibert, Armin; Gobrecht, Jens; Vandevondele, Joost; Ekinci, Yasin; van Bokhoven, Jeroen A.

    2017-01-01

    Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.

  7. Initial screening of thermal desorption for soil remediation

    Yezzi, J.J. Jr.; Tafuri, A.N.; Rosenthal, S.; Troxler, W.L.

    1994-01-01

    Petroleum-contaminated soils--caused by spills, leaks, and accidental discharges--exist at many sites throughout the United States. Thermal desorption technologies which are increasingly being employed to treat these soils, have met soil cleanup criteria for a variety of petroleum products. Currently the United States Environmental Protection Agency is finalizing a technical report entitled Use of Thermal Desorption for Treating Petroleum-Contaminated Soils to assist remedial project managers, site owners, remediation contractors, and equipment vendors in evaluating the use of thermal desorption technologies for petroleum-contaminated soil applications. The report will present a three-level screening method to help a reader predict the success of applying thermal desorption at a specific site. The objective of screening level one is to determine the likelihood of success in a specific application of thermal desorption. It will take into account procedures for collecting and evaluating data on site characteristics, contaminant characteristics, soil characteristics, and regulatory requirements. This level will establish whether or not thermal desorption should be evaluated further for site remediation, whether treatment should occur on-site or off-site, and if on-site is a viable option, what system size will be most cost-effective. The scope of this paper addresses only screening level one which provides a preliminary assessment of the applicability of thermal desorption to a particular site. This topic encompasses worksheets that are an integral part of the ''user friendly'' screening process. Level one screening provides a foundation for the subsequent two levels which follow a similar ''user friendly'' worksheet approach to evaluating thermal desorption technologies and establishing costs for thermal desorption in an overall remediation project

  8. Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

    Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

    2016-07-01

    The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

  9. Exchange of deuterium with hydrogen of zeolite catalyst surface

    Minachev, Kh.M.; Dmitriev, R.V.; Penchev, V.; Kanazirev, V.; Minchev, Kh.; Kasimov, Ch.K.; Bylgarska Akademiya na Naukite, Sofia. Inst. za Obshta i Organichna Khimiya; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

    1981-01-01

    Isotope heteromolecular exchange of hydrogen on the reduced nickel-containing zeolites takes places at the temperatures above 100 deg and it is controlled by activated hydrogen transfer from metal particles on the substrate surface. High-temperature redox treatment of nickel-containing zeolites results in the formation of large nickel crystallites on zeolite external faces. The rest part of nickel remains in zeolite pores and conditions a high promoting effect in the exchange reaction. Catalytic activity of reduced zeolites NiCaNaY in toluene disproportionation increases considerably only in the cases when nickel is introduced into zeolite by means of ion exchange. Close spatial location of nickel particles and OH groups promotes the procedure of both isotope exchange and disproportionation of toluene [ru

  10. Hydrogen passivation of electron trap in amorphous In-Ga-Zn-O thin-film transistors

    Hanyu, Yuichiro; Domen, Kay; Nomura, Kenji; Hiramatsu, Hidenori; Kamiya, Toshio; Kumomi, Hideya; Hosono, Hideo

    2013-01-01

    We report an experimental evidence that some hydrogens passivate electron traps in an amorphous oxide semiconductor, a-In-Ga-Zn-O (a-IGZO). The a-IGZO thin-film transistors (TFTs) annealed at 300 °C exhibit good operation characteristics; while those annealed at ≥400 °C show deteriorated ones. Thermal desorption spectra (TDS) of H 2 O indicate that this threshold annealing temperature corresponds to depletion of H 2 O desorption from the a-IGZO layer. Hydrogen re-doping by wet oxygen annealing recovers the good TFT characteristic. The hydrogens responsible for this passivation have specific binding energies corresponding to the desorption temperatures of 300–430 °C. A plausible structural model is suggested

  11. Hydrogen passivation of electron trap in amorphous In-Ga-Zn-O thin-film transistors

    Hanyu, Yuichiro, E-mail: y-hanyu@lucid.msl.titech.ac.jp; Domen, Kay [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama (Japan); Nomura, Kenji [Frontier Research Center, Tokyo Institute of Technology, Yokohama (Japan); Hiramatsu, Hidenori; Kamiya, Toshio [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama (Japan); Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama (Japan); Kumomi, Hideya [Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama (Japan); Hosono, Hideo [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama (Japan); Frontier Research Center, Tokyo Institute of Technology, Yokohama (Japan); Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama (Japan)

    2013-11-11

    We report an experimental evidence that some hydrogens passivate electron traps in an amorphous oxide semiconductor, a-In-Ga-Zn-O (a-IGZO). The a-IGZO thin-film transistors (TFTs) annealed at 300 °C exhibit good operation characteristics; while those annealed at ≥400 °C show deteriorated ones. Thermal desorption spectra (TDS) of H{sub 2}O indicate that this threshold annealing temperature corresponds to depletion of H{sub 2}O desorption from the a-IGZO layer. Hydrogen re-doping by wet oxygen annealing recovers the good TFT characteristic. The hydrogens responsible for this passivation have specific binding energies corresponding to the desorption temperatures of 300–430 °C. A plausible structural model is suggested.

  12. Sorption and desorption of diuron in Oxisol under biochar application

    Petter, Fabiano André; Ferreira, Tamara Santos; Sinhorin, Adilson Paulo; Lima, Larissa Borges de; Morais, Leidimar Alves de; Pacheco, Leandro Pereira

    2016-01-01

    ABSTRACT The objective of this study was to verify the kinetics of sorption and desorption of diuron in an Oxisol under application of biochar. The samples were collected in a field experiment conducted in randomized design blocks consisted of 2 base fertilization levels (0 and 400 kg∙ha−1 NPK 00-20-20 fertilizer formula) and 3 doses of biochar (0, 8 and 16 Mg∙ha−1). In the evaluation of sorption and desorption, Batch Equilibrium method was used. The kinetics of sorption and desorption of diu...

  13. Inelastic surface collisions and the desorption of massive molecular ions

    Macfarlane, R D [Texas A and M Univ., College Station (USA). Dept. of Chemistry

    1983-01-01

    The interaction of high energy ions in the region of electronic stopping (1 MeV u/sup -1/) stimulates the desorption of massive molecular ions of biomolecules such as insulin. The experimental details of the measurements are given with some examples of application for analytical mass spectrometry. Studies on the role of the incident ion (accelerator beam experiments) are reviewed as well as the contribution of the matrix to the desorption-ionization process. How the electronic relaxation process couples to desorption-ionization is a central question in understanding the overall mechanism of the process.

  14. 42 CFR 412.106 - Special treatment: Hospitals that serve a disproportionate share of low-income patients.

    2010-10-01

    ... to the hospital's DRG revenue for inpatient operating costs based on DRG-adjusted prospective payment... in paragraph (c) of this section. (c) Criteria for classification. A hospital is classified as a... section, if a hospital serves a disproportionate number of low-income patients, its DRG revenues for...

  15. Determination of diffusible and total hydrogen concentration in coated and uncoated steel

    Mabho, Nonhlangabezo

    2010-09-23

    The new trend in the steel industry demands thin, flexible, high strength steels with low internal embrittlement. It is a well known fact that the atomic hydrogen which is picked up during production, fabrication and service embrittles the steel. This has led to an extensive research towards the improvement of the quality of metallic materials by focusing on total and diffusible hydrogen concentrations which are responsible for hydrogen embrittlement. Since the internal embrittlement cannot be foreseen, the concentrations of diffusible hydrogen work as indicators while the total hydrogen characterizes the absorbed quantities and quality of that particular product. To meet these requirements, the analytical chemistry methods which include the already existing carrier gas melt (fusion) extraction methods that use infrared and thermal conductivity for total hydrogen detection were applied. The newly constructed carrier gas thermal desorption mass spectroscopy was applied to monitor the diffusible concentration at specific temperatures and desorption rates of hydrogen which will contribute towards the quality of materials during service. The TDMS method also involved the characterization of the energy quantity (activation energy) required by hydrogen to be removed from traps of which irreversible traps are preferred because they enhance the stability of the product by inhibiting the mobility of hydrogen which is detrimental to the metallic structures. The instrumentation for TDMS is quite simple, compact, costs less and applicable to routine analysis. To determine total and diffusible hydrogen, the influence of the following processes: chemical and mechanical zinc coating removal, sample cleaning with organic solvents, conditions for hydrogen absorption by electrolytic hydrogen charging, conditions of hydrogen desorption by storing the sample at room temperature, solid CO{sub 2} and at temperatures of the drier was analysed. The contribution of steel alloys towards

  16. Optimizing a High-Temperature Hydrogen Co-generation Reactor for Both Economic and Environmental Performance

    Weimar, Mark R.; Wood, Thomas W.; Reichmuth, Barbara A.; Johnson, Wayne L.

    2003-01-01

    This paper analyzes outcomes for a 3000 MWt High Temperature Gas Reaction nuclear power plant, given price and cost assumptions, and determined what level of hydrogen and electricity production would optimize the plant economically and environmentally (carbon reduction). The tradeoff between producing hydrogen through steam methane reformation and producing electricity is so disproportionate, that advanced reactors will likely be used only as peaking plants for electricity unless policymakers intervene with incentives to change the mix of electricity and hydrogen. The magnitude of the increase in electric prices or decrease in hydrogen prices required to allow electricity production indicate that substantial error in cost estimates would be required to change our analysis.

  17. Preparation of Mg2FeH6 Nanoparticles for Hydrogen Storage Properties

    N. A. Niaz

    2013-01-01

    Full Text Available Magnesium (Mg and iron (Fe nanoparticles are prepared by thermal decomposition of bipyridyl complexes of metals. These prepared Mg-Fe (2 : 1 nanoparticles are hydrogenated under 4 MPa hydrogen pressure and 673 K for 48 hours to achieve Mg2FeH6. Their structural analysis was assessed by applying manifold techniques. The hydrogen storage properties of prepared compound were measured by Sieverts type apparatus. The desorption kinetics were measured by high pressure thermal desorption spectrometer (HP-TDS. More than 5 wt% hydrogen released was obtained by the Mg2FeH6 within 5 min, and during rehydrogenation very effective hydrogen absorption rate was observed by the compound.

  18. Zero-Headspace Coal-Core Gas Desorption Canister, Revised Desorption Data Analysis Spreadsheets and a Dry Canister Heating System

    Barker, Charles E.; Dallegge, Todd A.

    2005-01-01

    Coal desorption techniques typically use the U.S. Bureau of Mines (USBM) canister-desorption method as described by Diamond and Levine (1981), Close and Erwin (1989), Ryan and Dawson (1993), McLennan and others (1994), Mavor and Nelson (1997) and Diamond and Schatzel (1998). However, the coal desorption canister designs historically used with this method have an inherent flaw that allows a significant gas-filled headspace bubble to remain in the canister that later has to be compensated for by correcting the measured desorbed gas volume with a mathematical headspace volume correction (McLennan and others, 1994; Mavor and Nelson, 1997).

  19. Global warming may disproportionately affect larger adults in a predatory coral reef fish

    Messmer, Vanessa

    2016-11-03

    Global warming is expected to reduce body sizes of ectothermic animals. Although the underlying mechanisms of size reductions remain poorly understood, effects appear stronger at latitudinal extremes (poles and tropics) and in aquatic rather than terrestrial systems. To shed light on this phenomenon, we examined the size dependence of critical thermal maxima (CTmax) and aerobic metabolism in a commercially important tropical reef fish, the leopard coral grouper (Plectropomus leopardus) following acclimation to current-day (28.5 °C) vs. projected end-of-century (33 °C) summer temperatures for the northern Great Barrier Reef (GBR). CTmax declined from 38.3 to 37.5 °C with increasing body mass in adult fish (0.45-2.82 kg), indicating that larger individuals are more thermally sensitive than smaller conspecifics. This may be explained by a restricted capacity for large fish to increase mass-specific maximum metabolic rate (MMR) at 33 °C compared with 28.5 °C. Indeed, temperature influenced the relationship between metabolism and body mass (0.02-2.38 kg), whereby the scaling exponent for MMR increased from 0.74 ± 0.02 at 28.5 °C to 0.79 ± 0.01 at 33 °C, and the corresponding exponents for standard metabolic rate (SMR) were 0.75 ± 0.04 and 0.80 ± 0.03. The increase in metabolic scaling exponents at higher temperatures suggests that energy budgets may be disproportionately impacted in larger fish and contribute to reduced maximum adult size. Such climate-induced reductions in body size would have important ramifications for fisheries productivity, but are also likely to have knock-on effects for trophodynamics and functioning of ecosystems.

  20. Disproportionate body composition and neonatal outcome in offspring of mothers with and without gestational diabetes mellitus.

    Persson, Martina; Fadl, Helena; Hanson, Ulf; Pasupathy, Dharmintra

    2013-11-01

    High birth weight is a risk factor for neonatal complications. It is not known if the risk differs with body proportionality. The primary aim of this study was to determine the risk of adverse pregnancy outcome in relation to body proportionality in large-for-gestational-age (LGA) infants stratified by maternal gestational diabetes mellitus (GDM). Population-based study of all LGA (birth weight [BW] >90th percentile) infants born to women with GDM (n = 1,547) in 1998-2007. The reference group comprised LGA infants (n = 83,493) born to mothers without diabetes. Data were obtained from the Swedish Birth Registry. Infants were categorized as proportionate (P-LGA) if ponderal index (PI) (BW in grams/length in cm(3)) was ≤90th percentile and as disproportionate (D-LGA) if PI >90th percentile. The primary outcome was a composite morbidity: Apgar score 0-3 at 5 min, birth trauma, respiratory disorders, hypoglycemia, or hyperbilirubinemia. Logistic regression analysis was used to obtain odds ratios (ORs) for adverse outcomes. The risk of composite neonatal morbidity was increased in GDM pregnancies versus control subjects but comparable between P- and D-LGA in both groups. D-LGA infants born to mothers without diabetes had significantly increased risk of birth trauma (OR 1.19 [95% CI 1.09-1.30]) and hypoglycemia (1.23 [1.11-1.37]). D-LGA infants in both groups had significantly increased odds of Cesarean section. The risk of composite neonatal morbidity is significantly increased in GDM offspring. In pregnancies both with and without GDM, the risk of composite neonatal morbidity is comparable between P- and D-LGA.

  1. Disproportionate Declines in Ground-Foraging Insectivorous Birds after Mistletoe Removal.

    David M Watson

    Full Text Available Insectivorous birds have been recognized as disproportionately sensitive to land-use intensification and habitat loss, with those species feeding primarily on the ground exhibiting some of the most dramatic declines. Altered litter inputs and availability of epigeic arthropods have been suggested to underlie reduced abundances and shrinking distributions but direct evidence is lacking. I used a patch-scale removal experiment in southern Australia to evaluate whether ground-feeding insectivores are especially vulnerable to altered litter-fall. Building on work demonstrating the importance of mistletoe litter to nutrient dynamics, litter was reduced by removing mistletoe (Loranthaceae from one set of eucalypt woodlands, responses of birds three years after mistletoe removal compared with otherwise similar control woodlands containing mistletoe. Despite not feeding on mistletoes directly, insectivores exhibited the greatest response to mistletoe removal. Among woodland residents, ground-foraging insectivores showed the most dramatic response; treatment woodlands losing an average of 37.4% of their pre-treatment species richness. Once these 19 species of ground-foraging insectivores were excluded, remaining woodland species showed no significant effect of mistletoe removal. This response reflects greater initial losses in treatment woodlands during the study (which coincided with a severe drought and double the number of species returning to control woodlands (where mistletoe numbers and litter were not manipulated post-drought. These findings support the productivity-based explanation of declining insectivores, suggesting diminished litter-fall reduced habitat quality for these birds via decreased availability of their preferred prey. In addition to altered prey availability, interactions between litter-fall and epigeic arthropods exemplify the importance of below-ground / above-ground linkages driving ecosystem function.

  2. The disproportionate high risk of HIV infection among the urban poor in sub-Saharan Africa.

    Magadi, Monica A

    2013-06-01

    The link between HIV infection and poverty in sub-Saharan Africa (SSA) is rather complex and findings from previous studies remain inconsistent. While some argue that poverty increases vulnerability, existing empirical evidence largely support the view that wealthier men and women have higher prevalence of HIV. In this paper, we examine the association between HIV infection and urban poverty in SSA, paying particular attention to differences in risk factors of HIV infection between the urban poor and non-poor. The study is based on secondary analysis of data from the Demographic and Health Surveys from 20 countries in SSA, conducted during 2003-2008. We apply multilevel logistic regression models, allowing the urban poverty risk factor to vary across countries to establish the extent to which the observed patterns are generalizable across countries in the SSA region. The results reveal that the urban poor in SSA have significantly higher odds of HIV infection than their urban non-poor counterparts, despite poverty being associated with a significantly lower risk among rural residents. Furthermore, the gender disparity in HIV infection (i.e. the disproportionate higher risk among women) is amplified among the urban poor. The paper confirms that the public health consequence of urban poverty that has been well documented in previous studies with respect to maternal and child health outcomes does apply to the risk of HIV infection. The positive association between household wealth and HIV prevalence observed in previous studies largely reflects the situation in the rural areas where the majority of the SSA populations reside.

  3. Global warming may disproportionately affect larger adults in a predatory coral reef fish.

    Messmer, Vanessa; Pratchett, Morgan S; Hoey, Andrew S; Tobin, Andrew J; Coker, Darren J; Cooke, Steven J; Clark, Timothy D

    2017-06-01

    Global warming is expected to reduce body sizes of ectothermic animals. Although the underlying mechanisms of size reductions remain poorly understood, effects appear stronger at latitudinal extremes (poles and tropics) and in aquatic rather than terrestrial systems. To shed light on this phenomenon, we examined the size dependence of critical thermal maxima (CTmax) and aerobic metabolism in a commercially important tropical reef fish, the leopard coral grouper (Plectropomus leopardus) following acclimation to current-day (28.5 °C) vs. projected end-of-century (33 °C) summer temperatures for the northern Great Barrier Reef (GBR). CTmax declined from 38.3 to 37.5 °C with increasing body mass in adult fish (0.45-2.82 kg), indicating that larger individuals are more thermally sensitive than smaller conspecifics. This may be explained by a restricted capacity for large fish to increase mass-specific maximum metabolic rate (MMR) at 33 °C compared with 28.5 °C. Indeed, temperature influenced the relationship between metabolism and body mass (0.02-2.38 kg), whereby the scaling exponent for MMR increased from 0.74 ± 0.02 at 28.5 °C to 0.79 ± 0.01 at 33 °C, and the corresponding exponents for standard metabolic rate (SMR) were 0.75 ± 0.04 and 0.80 ± 0.03. The increase in metabolic scaling exponents at higher temperatures suggests that energy budgets may be disproportionately impacted in larger fish and contribute to reduced maximum adult size. Such climate-induced reductions in body size would have important ramifications for fisheries productivity, but are also likely to have knock-on effects for trophodynamics and functioning of ecosystems. © 2016 John Wiley & Sons Ltd.

  4. Production of electronic grade lunar silicon by disproportionation of silicon difluoride

    Agosto, William N.

    1993-01-01

    Waldron has proposed to extract lunar silicon by sodium reduction of sodium fluorosilicate derived from reacting sodium fluoride with lunar silicon tetrafluoride. Silicon tetrafluoride is obtained by the action of hydrofluoric acid on lunar silicates. While these reactions are well understood, the resulting lunar silicon is not likely to meet electronic specifications of 5 nines purity. Dale and Margrave have shown that silicon difluoride can be obtained by the action of silicon tetrafluoride on elemental silicon at elevated temperatures (1100-1200 C) and low pressures (1-2 torr). The resulting silicon difluoride will then spontaneously disproportionate into hyperpure silicon and silicon tetrafluoride in vacuum at approximately 400 C. On its own merits, silicon difluoride polymerizes into a tough waxy solid in the temperature range from liquid nitrogen to about 100 C. It is the silicon analog of teflon. Silicon difluoride ignites in moist air but is stable under lunar surface conditions and may prove to be a valuable industrial material that is largely lunar derived for lunar surface applications. The most effective driver for lunar industrialization may be the prospects for industrial space solar power systems in orbit or on the moon that are built with lunar materials. Such systems would require large quantities of electronic grade silicon or compound semiconductors for photovoltaics and electronic controls. Since silicon is the most abundant semimetal in the silicate portion of any solar system rock (approximately 20 wt percent), lunar silicon production is bound to be an important process in such a solar power project. The lunar silicon extraction process is discussed.

  5. Global warming may disproportionately affect larger adults in a predatory coral reef fish

    Messmer, Vanessa; Pratchett, Morgan S.; Hoey, Andrew S.; Tobin, Andrew J.; Coker, Darren James; Cooke, Steven J.; Clark, Timothy D.

    2016-01-01

    Global warming is expected to reduce body sizes of ectothermic animals. Although the underlying mechanisms of size reductions remain poorly understood, effects appear stronger at latitudinal extremes (poles and tropics) and in aquatic rather than terrestrial systems. To shed light on this phenomenon, we examined the size dependence of critical thermal maxima (CTmax) and aerobic metabolism in a commercially important tropical reef fish, the leopard coral grouper (Plectropomus leopardus) following acclimation to current-day (28.5 °C) vs. projected end-of-century (33 °C) summer temperatures for the northern Great Barrier Reef (GBR). CTmax declined from 38.3 to 37.5 °C with increasing body mass in adult fish (0.45-2.82 kg), indicating that larger individuals are more thermally sensitive than smaller conspecifics. This may be explained by a restricted capacity for large fish to increase mass-specific maximum metabolic rate (MMR) at 33 °C compared with 28.5 °C. Indeed, temperature influenced the relationship between metabolism and body mass (0.02-2.38 kg), whereby the scaling exponent for MMR increased from 0.74 ± 0.02 at 28.5 °C to 0.79 ± 0.01 at 33 °C, and the corresponding exponents for standard metabolic rate (SMR) were 0.75 ± 0.04 and 0.80 ± 0.03. The increase in metabolic scaling exponents at higher temperatures suggests that energy budgets may be disproportionately impacted in larger fish and contribute to reduced maximum adult size. Such climate-induced reductions in body size would have important ramifications for fisheries productivity, but are also likely to have knock-on effects for trophodynamics and functioning of ecosystems.

  6. Medicare's Hospital Readmissions Reduction Program in Surgery May Disproportionately Affect Minority-serving Hospitals.

    Shih, Terry; Ryan, Andrew M; Gonzalez, Andrew A; Dimick, Justin B

    2015-06-01

    To project readmission penalties for hospitals performing cardiac surgery and examine how these penalties will affect minority-serving hospitals. The Hospital Readmissions Reduction Program will potentially expand penalties for higher-than-predicted readmission rates to cardiac procedures in the near future. The impact of these penalties on minority-serving hospitals is unknown. We examined national Medicare beneficiaries undergoing coronary artery bypass grafting in 2008 to 2010 (N = 255,250 patients, 1186 hospitals). Using hierarchical logistic regression, we calculated hospital observed-to-expected readmission ratios. Hospital penalties were projected according to the Hospital Readmissions Reduction Program formula using only coronary artery bypass grafting readmissions with a 3% maximum penalty of total Medicare revenue. Hospitals were classified into quintiles according to proportion of black patients treated. Minority-serving hospitals were defined as hospitals in the top quintile whereas non-minority-serving hospitals were those in the bottom quintile. Projected readmission penalties were compared across quintiles. Forty-seven percent of hospitals (559 of 1186) were projected to be assessed a penalty. Twenty-eight percent of hospitals (330 of 1186) would be penalized less than 1% of total Medicare revenue whereas 5% of hospitals (55 of 1186) would receive the maximum 3% penalty. Minority-serving hospitals were almost twice as likely to be penalized than non-minority-serving hospitals (61% vs 32%) and were projected almost triple the reductions in reimbursement ($112 million vs $41 million). Minority-serving hospitals would disproportionately bear the burden of readmission penalties if expanded to include cardiac surgery. Given these hospitals' narrow profit margins, readmission penalties may have a profound impact on these hospitals' ability to care for disadvantaged patients.

  7. Laser desorption mass spectrometry for biomolecule detection and its applications

    Winston Chen, C. H.; Sammartano, L. J.; Isola, N. R.; Allman, S. L.

    2001-08-01

    During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications.

  8. Laser desorption mass spectrometry for biomolecule detection and its applications

    Winston Chen, C.H.; Allman, S.L.; Sammartano, L.J.; Isola, N.R.

    2001-01-01

    During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications

  9. Improving of understanding of beta-hexachlorocyclohexane (HCH) adsorption on activated carbons by temperature-programmed desorption studies.

    Passé-Coutrin, Nady; Maisonneuve, Laetitia; Durimel, Axelle; Dentzer, Joseph; Gadiou, Roger; Gaspard, Sarra

    2016-01-01

    In order to understand the interactions between beta-hexachlorocyclohexane (HCH) and chemical groups at activated carbon (AC) surface, the solid samples were hydrogenated aiming to decrease the amounts of oxygenated groups. Two AC samples designated by BagH2O and BagP1.5 were prepared by water vapor activation and phosphoric acid activation, respectively, of sugarcane bagasse used as an AC precursor. A more simple molecule 1,2,3-trichloropropane (TCP) is used as a model of chlorinated compound. The AC were characterized by infrared, X-ray photoelectron spectroscopy (XPS), Raman resonance spectroscopies, as well as temperature-programmed desorption coupled with mass spectrometry (TPD-MS). BagP1.5 and BagH2O AC surface contained oxygenated groups. Upon hydrogenation, a decrease of most of these group amxounts was observed for both samples, while hydroxyl groups increased. On the basis of temperature-programmed desorption data obtained for AC samples contaminated with TCP or HCH, it was possible to determine the type of hydrogen bond formed between each AC and HCH.

  10. Nanodiamond for hydrogen storage: temperature-dependent hydrogenation and charge-induced dehydrogenation.

    Lai, Lin; Barnard, Amanda S

    2012-02-21

    Carbon-based hydrogen storage materials are one of hottest research topics in materials science. Although the majority of studies focus on highly porous loosely bound systems, these systems have various limitations including use at elevated temperature. Here we propose, based on computer simulations, that diamond nanoparticles may provide a new promising high temperature candidate with a moderate storage capacity, but good potential for recyclability. The hydrogenation of nanodiamonds is found to be easily achieved, in agreement with experiments, though we find the stability of hydrogenation is dependent on the morphology of nanodiamonds and surrounding environment. Hydrogenation is thermodynamically favourable even at high temperature in pure hydrogen, ammonia, and methane gas reservoirs, whereas water vapour can help to reduce the energy barrier for desorption. The greatest challenge in using this material is the breaking of the strong covalent C-H bonds, and we have identified that the spontaneous release of atomic hydrogen may be achieved through charging of hydrogenated nanodiamonds. If the degree of induced charge is properly controlled, the integrity of the host nanodiamond is maintained, which indicates that an efficient and recyclable approach for hydrogen release may be possible. This journal is © The Royal Society of Chemistry 2012

  11. Adsorption/desorption kinetics of Na atoms on reconstructed Si (111)-7 x 7 surface

    Chauhan, Amit Kumar Singh; Govind; Shivaprasad, S.M.

    2010-01-01

    Self-assembled nanostructures on a periodic template are fundamentally and technologically important as they put forward the possibility to fabricate and pattern micro/nano-electronics for sensors, ultra high-density memories and nanocatalysts. Alkali-metal (AM) nanostructure grown on a semiconductor surface has received considerable attention because of their simple hydrogen like electronic structure. However, little efforts have been made to understand the fundamental aspects of the growth mechanism of self-assembled nanostructures of AM on semiconductor surfaces. In this paper, we report organized investigation of kinetically controlled room-temperature (RT) adsorption/desorption of sodium (Na) metal atoms on clean reconstructed Si (111)-7 x 7 surface, by X-ray photoelectron spectroscopy (XPS). The RT uptake curve shows a layer-by-layer growth (Frank-vander Merve growth) mode of Na on Si (111)-7 x 7 surfaces and a shift is observed in the binding energy position of Na (1s) spectra. The thermal stability of the Na/Si (111) system was inspected by annealing the system to higher substrate temperatures. Within a temperature range from RT to 350 o C, the temperature induced mobility to the excess Na atoms sitting on top of the bilayer, allowing to arrange themselves. Na atoms desorbed over a wide temperature range of 370 o C, before depleting the Si (111) surface at temperature 720 o C. The acquired valence-band (VB) spectra during Na growth revealed the development of new electronic-states near the Fermi level and desorption leads the termination of these. For Na adsorption up to 2 monolayers, decrease in work function (-1.35 eV) was observed, whereas work function of the system monotonically increases with Na desorption from the Si surface as observed by other studies also. This kinetic and thermodynamic study of Na adsorbed Si (111)-7 x 7 system can be utilized in fabrication of sensors used in night vision devices.

  12. Study of chlordecone desorption from activated carbons and subsequent dechlorination by reduced cobalamin.

    Ranguin, Ronald; Durimel, Axelle; Karioua, Reeka; Gaspard, Sarra

    2017-11-01

    Since 1972, the French departments of Guadeloupe and Martinique have intensively used organochlorinated pesticides such as chlordecone (CLD) and hexachlorocyclohexane (HCH) isomers to prevent the proliferation of banana weevil (Cosmopolite sordidus). These molecules are stable in the environment, leading to a continuous contamination of soils, water, and food chain in the banana-producing areas. In these polluted areas, water treatment plants are equipped with activated carbon (AC) filters. In order to improve treatment of CLD-contaminated waters by AC, CLD adsorption and desorption kinetic studies are carried out using different ACs produced from sugar cane bagasse as adsorbents and subsequent CLD degradation is performed using reduced vitamin B12 (VB12). A GC-MS method for CLD quantification is as well optimized. This study shows that bagasse ACs are able to capture the pollutant, leading to a CLD concentration decrease from 1 to 73 μg L -1 , with an adsorption capacity of 162 μg mg -1 . Adsorption capacity increase with the temperature indicates an endothermic process. Polar solvents favor CLD desorption from ACs, suggesting hydrogen bonding between CLD and surface groups of ACs, the best solvent for chemical desorption being ethanol. Subsequent degradation of CLD in ethanol is performed using vitamin B12 reduced by either 1,4-dithiotreitol (DTT) or zerovalent zinc, leading to 90% of CLD removal and to the molecule cage structure opening for formation of a pentachloroindene intermediate product, characterized by GC MS/MS. A pathway for pentachloroindene formation from CLD is proposed.

  13. Desorption by Femtosecond Laser Pulses : An Electron-Hole Effect?

    D. M., NEWNS; T. F., HEINZ; J. A., MISEWICH; IBM Research Division, T. J. Watson Research Center; IBM Research Division, T. J. Watson Research Center; IBM Research Division, T. J. Watson Research Center

    1992-01-01

    Desorption of molecules from metal surfaces induced by femtosecond visible laser pulses has been reported. Since the lattice temperature rise is insufficient to explain desorption, an electronic mechanism is clearly responsible. It is shown that a theory based on direct coupling between the center-of-mass degree of freedom of the adsorbate and the electron-hole excitations of the substrate provides a satisfactory explanation of the various experimental findings.

  14. Questioning hydrogen

    Hammerschlag, Roel; Mazza, Patrick

    2005-01-01

    As an energy carrier, hydrogen is to be compared to electricity, the only widespread and viable alternative. When hydrogen is used to transmit renewable electricity, only 51% can reach the end user due to losses in electrolysis, hydrogen compression, and the fuel cell. In contrast, conventional electric storage technologies allow between 75% and 85% of the original electricity to be delivered. Even when hydrogen is extracted from gasified coal (with carbon sequestration) or from water cracked in high-temperature nuclear reactors, more of the primary energy reaches the end user if a conventional electric process is used instead. Hydrogen performs no better in mobile applications, where electric vehicles that are far closer to commercialization exceed fuel cell vehicles in efficiency, cost and performance. New, carbon-neutral energy can prevent twice the quantity of GHG's by displacing fossil electricity than it can by powering fuel cell vehicles. The same is true for new, natural gas energy. New energy resources should be used to displace high-GHG electric generation, not to manufacture hydrogen

  15. Desorption dynamics of deuterium in CuCrZr alloy

    Thi Nguyen, Lan Anh; Lee, Sanghwa; Noh, S. J.; Lee, S. K.; Park, M. C.; Shu, Wataru; Pitcher, Spencer; Torcy, David; Guillermain, David; Kim, Jaeyong

    2017-12-01

    Desorption behavior of deuterium (D2) in CuCrZr alloy was investigated considering sample thickness, loading and baking temperature of deuterium followed by the ITER scopes. Cylindrical specimens of 1, 3, 5 mm thick with 4 mm diameter were exposed to deuterium at a pressure of 25 bar at 120, 240 and 350 °C for 24 h, then baked at 800 °C in a vacuum chamber maintained at a pressure lower than 10-7 Torr. Deuterium desorption characteristics such as desorption rate and amount of deuterium in the sample were estimated by analyzing the desorption peaks monitored with a residual gas analyzer (RGA), and the trapping energy of deuterium was calculated using thermal desorption spectroscopy (TDS). Secondary ion mass spectroscopy (SIMS) results showed that deuterium atoms embedded in the sample at a depth of less than 15 μm and desorbed as low as 400 °C. All absorbed deuterium atoms in the specimen were completely retrieved by dynamic pumping at 800 °C in 15 min. The desorption rate of deuterium per unit area was inversely proportional to the increment of the thickness of the sample, and was proportional to the loading temperature. Based on the assumption that a uniform distribution of interstitial sites for deuterium follows the Femi-Dirac statistics, the result of TDS demonstrated that the CuCrZr alloy has two types of trapping energies, which were estimated to be 62 and 79 kJ/mol.

  16. Impact of neutron irradiation on thermal helium desorption from iron

    Hu, Xunxiang, E-mail: hux1@ornl.gov [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Field, Kevin G. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Taller, Stephen [University of Michigan, Ann Arbor, MI 48109 (United States); Katoh, Yutai [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Wirth, Brian D. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); University of Tennessee, Knoxville, TN 37996 (United States)

    2017-06-15

    The synergistic effect of neutron irradiation and transmutant helium production is an important concern for the application of iron-based alloys as structural materials in fission and fusion reactors. In this study, we investigated the impact of neutron irradiation on thermal helium desorption behavior in high purity iron. Single crystalline and polycrystalline iron samples were neutron irradiated in HFIR to 5 dpa at 300 °C and in BOR-60 to 16.6 dpa at 386 °C, respectively. Following neutron irradiation, 10 keV He ion implantation was performed at room temperature on both samples to a fluence of 7 × 10{sup 18} He/m{sup 2}. Thermal desorption spectrometry (TDS) was conducted to assess the helium diffusion and clustering kinetics by analyzing the desorption spectra. The comparison of He desorption spectra between unirradiated and neutron irradiated samples showed that the major He desorption peaks shift to higher temperatures for the neutron-irradiated iron samples, implying that strong trapping sites for He were produced during neutron irradiation, which appeared to be nm-sized cavities through TEM examination. The underlying mechanisms controlling the helium trapping and desorption behavior were deduced by assessing changes in the microstructure, as characterized by TEM, of the neutron irradiated samples before and after TDS measurements.

  17. Reaction dynamics of molecular hydrogen on silicon surfaces

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  18. Thermal desorption and bombardment-induced release of deuterium implanted into stainless steels at low energy

    Farrell, G.; Donnelly, S.E.

    1978-01-01

    Thermal desorption spectra have been obtained for low energy (15-750 eV) deuterons implanted into types 321 and 304 stainless steel, to total fluences in the range 10 13 - 10 17 deuterons/cm 2 . In each case the spectra show a peak at about 350 K, but in the 321 steel there is a second peak in the region of 900 K, the population and peak temperature of which increase with energy. Activation energies of 0.99 and 2.39 eV and a rate constant of 7 x 10 15 /s have been derived for the peaks and it is thought that the first peak corresponds to release from sites close to the surface, while the second peak may be related to trapping at impurities such as Ti. Measurements have also been made of the release of deuterium resulting from post-implantation bombardment with hydrogen ions. It is found that depletion of the first peak in the 321 steel is the result of gas sputtering, but depletion of the second peak is the result of the formation of HD during desorption, while depletion of the peak in the 304 stainless steel also results from HD formation even though this peak is the same as the first peak in the 321 steel. Estimates have also been made of the deuterium self-sputtering cross section at various energies, which show a monotonic decrease as energy increases. (Auth.)

  19. Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

    Lixia Zhao; Yifeng Zhang; Shuhong Fang; Lingyan Zhu; Zhengtao Liu

    2014-01-01

    The sorption and desorption behaviors of two perfluoroalkane sulfonates (PFSAs),including perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) on two humic acids (HAs) and humin (HM),which were extracted from a peat soil,were investigated.The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances (HSs) was much higher than PFHxS.For the same PFSA compound,the sorption on HSs followed the order of HM > HA2 > HA1.These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs.The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity,but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs.Compared to PFOS,PFHxS displayed distinct desorption hysteresis,probably due to irreversible pore deformation after sorption of PFHxS.The sorption of the two PFSAs on HSs decreased with an increase in pH in the solution.This is ascribed to the electrostatic interaction and hydrogen bonding at lower pH.Hydrophobic interaction might also be stronger at lower pH due to the aggregation of HSs.

  20. Particle desorption mass spectrometric surface characterization

    Summers, W.R.

    1986-01-01

    The feasibility of utilizing 252 Cf-Particle Desorption Mass Spectrometry (PDMS) to characterize the surface region of solid samples has been evaluated. The PDMS experiment was adapted to an ultrahigh vacuum (UHV) environment and was configured so as to allow the analysis of thick as well as thin samples. This apparatus included an in situ sputter cleaning/depth profiling facility. The mass resolution was variable from 300 to 200 at 133 daltons by changing the drift length from 27 cm to 20 cm. Desorbed ions were focused by using either a dual grid assembly or an einzel lens. The overall instrumental transmission efficiency with the einzel lens operative was approximately 50%. The applicability of 252 Cf-PDMS to samples that were thick and insulating was demonstrated in the analysis of geological specimens. Pollucite, Microcline, Amblygonite, and Lepidolite were analyzed without complications associated with sample thickness or charge accumulation. Substitution occurring between the alkali metals in the environment was observed by PDMS and was corroborated by SIMS, XPS, and EMP analyses. The analysis of NBM SRM glasses addressed the suitability of combining the PDMS technique was sputter etching. This application demonstrated the ability of this technique to sense changes in the chemical environment brought about by sputter cleaning. The analysis of these samples also allowed the estimation of detection limits for lithium, rubidium, and cesium in a glass matrix as 300 ppm, 400 ppm, and 400 ppm, respectively. Sputter depth profiling combined with 252 Cf-PDMS analysis of an aluminum layer on a silicon substrate established the utility of the PDMS technique in surface characterization

  1. Hydrogenation of ethylene over PrCo5Hsub(2.4)

    Soga, Kazuo; Imamura, Hayao; Ikeda, Sakuji

    1977-01-01

    To elucidate the chemical reactivity of the hydrogen atom absorbed in the hydrogenated alloy PrCo 5 H sub(n), the hydrogenation of ethylene was carried out over PrCo 5 Hsub(2.4) in the absence (A) or presence (B) of hydrogen in gas phase. PrCo 5 Hsub(2.4) was prepared from PrCo 5 according to an ordinary procedure with repeated heating and cooling in hydrogen atmosphere. The hydrogenation of ethylene was conducted at about -70 0 C in a conventional gas circulation system in a pressure range of ethylene 5 -- 16 cmHg and hydrogen 0 -- 38.0 cmHg. The hydrogenation rate was followed by gas chromatography. In the case of (A), the total gas pressure in the gas phase remained constant during the reaction. The hydrogenation rate was independent of the partial pressure of ethylene and it increased in proportion to the concentration of the absorbed hydrogen atom. The rate of desorption of the absorbed hydrogen atom from PrCo 5 Hsub(2.4) also measured under a reduced pressure. The desorption rate was approximately the same as the hydrogenation rate under the similar conditions. From these results, it was concluded that the migration process of the absorbed hydrogen atom from the bulk of the alloy to its surface was rate-determining. In the case of (B), on the other hand, the hydrogenation rate was accelerated by the gaseous hydrogen; the rate increased almost linearly with increasing pressure of hydrogen. The hydrogenation of ethylene was also conducted over PrCo 5 under the similar conditions. (auth.)

  2. A micro-fabricated hydrogen storage module with sub-atmospheric activation and durability in air exposure

    Shan, Xi; Payer, Joe H. [Corrosion and Reliability Engineering, Department of Chemical and Biomolecular Engineering, University of Akron, 302 Buchtel Common, Akron, OH 44325 (United States); Wainright, Jesse S.; Dudik, Laurie [Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States)

    2011-01-15

    The objective of this work was to develop a hydrogen storage module for onboard electrical power sources suitable for use in micro-power systems and micro-electro-mechanical systems (MEMS). Hydrogen storage materials were developed as thin-film inks to be compatible with an integrated manufacturing process. Important design aspects were (a) ready activation at sub-atmospheric hydrogen pressure and room temperature and (b) durability, i.e. capable of hundreds of absorption/desorption cycles and resistance to deactivation on exposure to air. Inks with palladium-treated intermetallic hydrogen storage alloys were developed and are shown here to be compatible with a thin-film micro-fabrication process. These hydrogen storage modules absorb hydrogen readily at atmospheric pressure, and the absorption/desorption rates remained fast even after the ink was exposed to air for 47 weeks. (author)

  3. Evaluation of hydrogen trapping mechanisms during performance of different hydrogen fugacity in a lean duplex stainless steel

    Silverstein, R., E-mail: barrav@post.bgu.ac.il [Department of Material Science and Engineering, Ben-Gurion University of the Negev, Beer-Sheva (Israel); Eliezer, D. [Department of Material Science and Engineering, Ben-Gurion University of the Negev, Beer-Sheva (Israel); Glam, B.; Eliezer, S.; Moreno, D. [Soreq Nuclear Research Center, Yavne, 81800 (Israel)

    2015-11-05

    Hydrogen trapping behavior in a lean duplex stainless steel (LDS) is studied by means of thermal desorption spectrometry (TDS). The susceptibility of a metal to hydrogen embrittlement is directly related to the trap characteristics: source or sink (reversible or irreversible, respectively). Since trapping affects the metal's diffusivity, it has a major influence on the hydrogen assisted cracking (HAC) phenomenon. It is known from previously published works that the susceptibility will depend on the competition between reversible and irreversible traps; meaning a direct relation to the hydrogen's initial state in the steel. In this research the trapping mechanism of LDS, exposed to different hydrogen charging environments, is analyzed by means of TDS. The TDS analysis was supported and confirmed by means of X-ray diffraction (XRD), hydrogen quantitative measurements and microstructural observations. It was found that gaseous charging (which produces lower hydrogen fugacity) creates ∼22% higher activation energy for hydrogen trapping compared with cathodic charging (which produces higher hydrogen fugacity). These results are due to the different effects on the hydrogen behavior in LDS which causes a major difference in the hydrogen contents and different hydrogen assisted phase transitions. The highest activation energy value in the cathodic charged sample was ascribed to the dominant phase transformation of γ → γ{sup ∗}, whereas in the gaseous charged sample it was ascribed to the dominant formation of intermetallic compound, sigma (σ). The relation between hydrogen distribution in LDS and hydrogen trapping mechanism is discussed in details. - Highlights: • The relation between hydrogen distribution and trapping in LDS is discussed. • Hydrogen's initial state in LDS causes different microstructural changes. • Gaseous charged LDS creates higher trapping energy compared to cathodic charged LDS. • The dominant phase transformation in

  4. Direct isotope determination of isotopically labelled lipids by field desorption mass spectrometry

    Lehmann, W.D.; Kessler, M.

    1982-01-01

    Lipids labelled with deuterium or carbon-14 have been investigated by field desorption mass spectrometry for determination of their degree of labelling. This application is demonstrated for free fatty acids, cholesterol, cholesteryl esters, triglycerides, and L-α-phosphatidylcholines. Comparison of the molecular ion groups of the non-labelled and of the labelled compounds enables a fast and reliable determination of the degree of labelling. For multiply labelled compounds the label distribution is also obtained from the molecular ion group. In addition, for cholesteryl esters and for phosphatidylcholines structurally significant fragment ions provide information about the position of the label. Several hundred nanograms of the compound are typically required for a single analysis with a relative standard error of 0.5-2% in the value calculated for atom% hydrogen-2 or for the specific carbon-14 activity. (orig.) [de

  5. Laser-induced desorption determinations of surface diffusion on Rh(111)

    Seebauer, E.G.; Schmidt, L.D.

    1987-01-01

    Surface diffusion of hydrogen, deuterium and CO on Rh(111) has been investigated by laser-induced thermal desorption (LITD) and compared with previous results for these species on Pt(111) and on other metals. For deuterium in the coverage range 0.02 0 - 8 x 10 -2 cm 2 /s, with a diffusion activation energy 3.7 0 rises from 10 -3 to 10 -2 cm 2 /s between θ = 0.01 and 0.40. Values of E/sub diff/ on different surfaces appear to correlate with differences in heats of adsorption in different binding states which form saddle point configurations in surface diffusion. In addition, oxidation reactions on Rh and on several other transition metal surfaces may be limited to CO or H surface diffusion. 30 refs., 3 figs., 1 tab

  6. Plasma Desorption Mass Spectrometry using TANDEM accelerator in National Industrial Research Inst. of Nagoya

    Mizota, Takeshi; Nakao, Setsuo; Niwa, Hiroaki; Saito, Kazuo [Particle Beam Sceince Laboratory, Multi-Function Material Science Department, National Industrial Research Inst. of Nagoya, Nagoya (Japan)

    2001-02-01

    Plasma Desorption Mass Spectrometry (PDMS) analysis was studied using TANDEM accelerator. The heavy ions of MeV range emit the secondary ions of atoms, molecules, polymers and clusters from the irradiated samples without destruction. The analysis system of PDMS designed and set-up using a mass spectrometer of Time of Flight and the TANDEM accelerator. The system performance was tested for C-60 fullerene on the surface of the samples using 11.2 MeV {sup 28}Si beams produced by the TANDEM accelerator of 1.7MV. The result shows that the hydrogen and hydrocarbons can be analyzed in the range of 1amu unit. The resolution (M/{delta}M) of the Mass Spectrometry system is confirmed to be about 1000 from the separation of the 720 and 721amu peaks, which is attributed to the C-60 fullerene including {sup 13}C atoms. (H. Katsuta)

  7. Modelling for Near-Surface Transport Dynamics of Hydrogen of Plasma Facing Materials by use of Cellular Automaton

    Shimura, K.; Terai, T.; Yamawaki, M.

    2003-01-01

    In this study, the kinetics of desorption of adsorbed hydrogen from an ideal metallic surface is modelled in Cellular Automaton (CA). The modelling is achieved by downgrading the surface to one dimension. The model consists of two parts that are surface migration and desorption. The former is attained by randomly sorting the particles at each time, the latter is realised by modelling the thermally-activated process. For the verification of this model, thermal desorption is simulated then the comparison with the chemical kinetics is carried out. Excellent agreement is observed from the result. The results show that this model is reasonable to express the recombinative desorption of two chemisorbed adatoms. Though, the application of this model is limited to the second-order reaction case. But it can be believed that the groundwork of modelling the transport dynamics of hydrogen through the surface under complex conditions is established

  8. Hydrogen storage by functionalised Poly(ether ether ketone)

    Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

    2010-07-01

    In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

  9. New Transition metal assisted complex borohydrides for hydrogen storage

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  10. The Disproportionate and Potentially Negative Influence of Research Universities on the Quality of Geoscience Education

    Samson, P. J.

    2010-12-01

    There is a large and growing body of research indicating that post-secondary education in science, technology, engineering, and mathematics (STEM) fields is failing to prepare citizens for the 21st century economy. Introductory STEM courses are vital for preparing science majors for their fields of study and are the only exposure to science many college students will receive, but the quality of teaching in these courses is often not informed by research on teaching and learning. Research universities play an especially prominent role in the design of introductory courses. While research and doctoral universities account for only about 6% of all higher education institutions, they confer 32 per cent of the baccalaureate degrees, and 56 per cent of the baccalaureates earned by recent recipients of science and engineering doctorates. By assuming that larger introductory classes occur at research institutions one can estimate that a dominant number of students receiving introductory instruction in the geosciences are probably occurring at research institutions. Moreover, research universities produce the majority of tenure-track faculty who will later teach at four-year colleges, so the role of research institutions in the influence of introductory course design is expected to be disproportionately large. While introductory courses at research universities play a influential role in how such courses are designed, the teaching of introductory courses is too often viewed as an undesirable assignment for instructors at those institutions. The effort seems unrewarding with incentives for improving teaching at research institutions perceived as modest at best, if not negative. It is commonly perceived that teaching introductory courses will decrease opportunities for teaching higher-level courses to graduate students and/or to conduct research. Furthermore, even for those interested in improving their pedagogical methods, current approaches to professional development are

  11. Design concept for α-hydrogen-substituted nitroxides.

    Amar, Michal; Bar, Sukanta; Iron, Mark A; Toledo, Hila; Tumanskii, Boris; Shimon, Linda J W; Botoshansky, Mark; Fridman, Natalia; Szpilman, Alex M

    2015-02-06

    Stable nitroxides (nitroxyl radicals) have many essential and unique applications in chemistry, biology and medicine. However, the factors influencing their stability are still under investigation, and this hinders the design and development of new nitroxides. Nitroxides with tertiary alkyl groups are generally stable but obviously highly encumbered. In contrast, α-hydrogen-substituted nitroxides are generally inherently unstable and rapidly decompose. Herein, a novel, concept for the design of stable cyclic α-hydrogen nitroxides is described, and a proof-of-concept in the form of the facile synthesis and characterization of two diverse series of stable α-hydrogen nitroxides is presented. The stability of these unique α-hydrogen nitroxides is attributed to a combination of steric and stereoelectronic effects by which disproportionation is kinetically precluded. These stabilizing effects are achieved by the use of a nitroxide co-planar substituent in the γ-position of the backbone of the nitroxide. This premise is supported by a computational study, which provides insight into the disproportionation pathways of α-hydrogen nitroxides.

  12. Hydrogen Adsorption on Nanoporous Biocarbon

    Wood, M. B.; Burress, J. W.; Lapilli, C. M.; Pfeifer, P.; Shah, P. S.; Suppes, G. J.; Dillon, A. C.; Parilla, P. A.

    2007-03-01

    As a part of the Alliance for Collaborative Research in Alternative Fuel Technology (http://all-craft.missouri.edu) we study activated carbons made from corncob, optimized for storing methane and hydrogen (H2) by physisorption at low pressure. We report here: (a) storage capacities of 73-91 g H2/kg carbon at 77 K and 47 bar, validated in three different laboratories (the 2010 DOE target is 60 g H2/kg system); (b) binding energies from H2 adsorption isotherms (c) temperature-programmed desorption data; (d) degree of graphitization of the carbon surface from Raman spectra; (e) pore structure of carbon from nitrogen and methane adsorption isotherms, and small-angle x-ray scattering. The structural analysis shows that the carbon is highly microporous and that the pore space is highly correlated (micropores do not scatter independently).

  13. Activation of erbium films for hydrogen storage

    Brumbach, Michael T.; Ohlhausen, James A.; Zavadil, Kevin R.; Snow, Clark S.; Woicik, Joseph C.

    2011-01-01

    Hydriding of metals can be routinely performed at high temperature in a rich hydrogen atmosphere. Prior to the hydrogen loading process, a thermal activation procedure is required to promote facile hydrogen sorption into the metal. Despite the wide spread utilization of this activation procedure, little is known about the chemical and electronic changes that occur during activation and how this thermal pretreatment leads to increased rates of hydrogen uptake. This study utilized variable kinetic energy X-ray photoelectron spectroscopy to interrogate the changes during in situ thermal annealing of erbium films, with results confirmed by time-of-flight secondary ion mass spectrometry and low energy ion scattering. Activation can be identified by a large increase in photoemission between the valence band edge and the Fermi level and appears to occur over a two stage process. The first stage involves desorption of contaminants and recrystallization of the oxide, initially impeding hydrogen loading. Further heating overcomes the first stage and leads to degradation of the passive surface oxide leading to a bulk film more accessible for hydrogen loading.

  14. The electrochemical characteristics of Mg2Ni nanocrystalline hydrogen storage alloy

    Zhang Ling; Zhou Xiaosong; Peng Shuming

    2008-06-01

    The nanocrystalline Mg 2 Ni materials were prepared by mechanical alloying. The cyclic voltametry results indicated that the potential of oxidation peak was shift as the scan rate increased and the absorption property of Mg 2 Ni prepared by mechanical alloying was increased even at ambient temperature. The absorption and desorption of hydrogen in Mg 2 Ni alloy were remarkably accelerated with the rising temperature. Small angel X-ray scattering results indicated that the Mg 2 Ni powder have 1-5 nm and 5-10 nm particle size distribution, which increased the acting sites of hydrogen absorption/desorption reaction and decreased the diffusion path of hydrogen desorption. It was induced to the enhanced performance of Mg 2 Ni nanocrystalline powder. The cycle life investigated results indicated that the activation property of Mg 2 Ni nanocrystal-line hydrogen storage alloy electrode was excellent, the capacitance maintenance ration was 66% after 200 cycles. The coating of epoxy resin on one side of the electrode had no effect on the activation property and the capacitance maintenance ration was better than the uncoating one. But the anode peak current value and the cathodic peak current value were decreased remarkably which indicated that the hydrogen absorption/desorption rate and the charge/discharge degree had decreased. (authors)

  15. Disproportionation phenema of wistite phase in the model iron catalysts for ammonia synthesis studied by Moessbauer spectroscopy

    Pattek-Janczyk, A.; Miczko, B.

    1990-01-01

    A model iron catalysts for ammonia synthesis containing a large amount of wustite (35 wt%) has been studied during the annealing in an inert atmosphere in the temperature range of 573-773 K. Changes in magnetite and wustite phases were followed by Muessbauer spectroscopy (MS). Before starting the thermal treatment, two kinds of wustite of different structures have been found by MS and X-ray diffraction. The behaviour of both kinds of wustite during the annealing was different. One of them, closer to the stoichiometric compound, disproportionated at once into magnetite and iron; its content decreased systematically without changes in the Muessbauer parameters. In the second wustite, only qualitatieve changes were observed at first (its nonstoichiometry decreases without changes in content and, next, this phase started to disproportionate too. (auhtor). 31 refs.; 6 figs.; 2 tabs

  16. Hydrogen program overview

    Gronich, S. [Dept. of Energy, Washington, DC (United States). Office of Utility Technologies

    1997-12-31

    This paper consists of viewgraphs which summarize the following: Hydrogen program structure; Goals for hydrogen production research; Goals for hydrogen storage and utilization research; Technology validation; DOE technology validation activities supporting hydrogen pathways; Near-term opportunities for hydrogen; Market for hydrogen; and List of solicitation awards. It is concluded that a full transition toward a hydrogen economy can begin in the next decade.

  17. Adsorption and desorption dynamics of citric acid anions in soil

    Oburger, E.

    2011-07-26

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal uptake. Little is known about the interaction dynamics of organic acid anions with the soil matrix and the potential impact of adsorption and desorption processes on the functional significance of these effects. The aim of this study was to characterize experimentally the adsorption and desorption dynamics of organic acid anions in five agricultural soils differing in iron and aluminium oxide contents and using citrate as a model carboxylate. Results showed that both adsorption and desorption processes were fast in all soils, reaching a steady state within approximately 1 hour. However, for a given total soil citrate concentration (ct) the steady state was critically dependent on the starting conditions of the experiment, whether most of the citrate was initially present in solution (cl) or held on the solid phase (cs). Specifically, desorption-led processes resulted in significantly smaller steady-state solution concentrations than adsorption-led processes, indicating that hysteresis occurred. As it is not possible to distinguish between different adsorption and desorption pools in soil experimentally, a new dynamic hysteresis model that relies only on measured soil solution concentrations was developed. The model satisfactorily explained experimental data and was able to predict dynamic adsorption and desorption behaviour. To demonstrate its use, we applied the model to two relevant situations involving exudation and microbial degradation. The study highlighted the complex nature of citrate adsorption and desorption dynamics in soil. We conclude that existing models need to incorporate both temporal and hysteresis components to describe realistically the role and fate of organic acids in soil processes. © 2011 The

  18. Study of the influence of the temperature in the magnetic properties and in microstructure in the permanent magnets Pr-Fe-B-Nb-Co based obtained by hydrogen; Estudo da influencia da temperatura nas propriedades magneticas e na microestrutura nos imas permanentes a base de Pr-Fe-B-Nb-Co obtidos com hidrogenio

    Silva, Suelanny Carvalho da

    2007-07-01

    Fine magnetic powders were produced using the hydrogenation disproportionation desorption and recombination (HDDR) process. The first stage in this work involved an investigation of the effect of the Co content and range of desorption/ recombination temperatures between 800 and 900 deg C with the purpose of optimizing the HDDR treatment for Pr{sub 14}Fe{sub 80}B{sub 6} and Pr{sub 14}Fe{sub bal}Co{sub x}B{sub 6}Nb{sub 0,1} (x= 0, 4, 8, 10, 12, 16) alloys. The cast alloys were annealed at 1100 deg C for 20 hours for homogenization. The processing temperature (desorption/ recombination) affected the microstructure and magnetic properties of the bonded magnets. The alloy with low cobalt content (4 at.%) required the highest reaction temperature (880 deg C) to yield anisotropic bonded magnets. The optimum temperature for alloys with 8 at.% Co and 10 at.% Co were 840 deg C and 820 deg C, respectively. Alloys with high cobalt content (12 at.% and 16 at.%) were processed at 840 deg C. The optimum desorption temperature for achieving high anisotropy for Pr{sub 14}Fe{sub 80}B{sub 6} and Pr{sub 14}Fe{sub 79,9}B{sub 6}Nb{sub 0,1} was 820 deg C. The best remanence (862 mT) was achieved with the Pr{sub 14}Fe{sub 67,9}B{sub 6}Co{sub 12}Nb{sub 0,1} magnet, processed at 840 deg C. Each alloy required an optimum reaction temperature and exhibited a particular microstructure according to the composition. The second stage of the work involved the characterization, for each temperature, of the Pr{sub 14}Fe{sub 80}B{sub 6} HDDR powder processed using X-ray diffraction analysis. The samples of the HDDR material were studied by synchrotron radiation powder diffraction using the Rietveld method for cell refinement, phase quantification and crystallite sizes determination. Scanning electron microscopy has also been employed to reveal the morphology of the HDDR powder. (author)

  19. The effect of compositional changes on the structural and hydrogen storage properties of (La–Ce)Ni5 type intermetallics towards compounds suitable for metal hydride hydrogen compression

    Odysseos, M.; De Rango, P.; Christodoulou, C.N.; Hlil, E.K.; Steriotis, T.; Karagiorgis, G.; Charalambopoulou, G.; Papapanagiotou, T.; Ampoumogli, A.; Psycharis, V.; Koultoukis, E.; Fruchart, D.; Stubos, A.

    2013-01-01

    Graphical abstract: The effect of the partial substitution of La with Ce on the crystal structure and the final hydrogen storage properties of the alloys. Highlights: ► Absorption-based systems exploit the properties of reversible metal hydrides. ► AB5 intermetallics are mostly popular for thermal desorption compressors. ► Investigation of H2 absorption/desorption properties of LaNi5 and its derivatives. ► LaNi5 thermodynamic properties adjustment by partially replacing La with rare earths. -- Abstract: The present work has been aiming at the synthesis and study of a series of La 1−x Ce x Ni 5 (x = 0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8) alloys in an attempt to investigate possible alterations of the hydrogen absorption/desorption properties The alloys were prepared by induction melting of the constituent elements. The systematic characterization of all new compounds by means of XRD and hydrogen sorption measurements revealed the effect of the partial substitution of La with Ce on the crystal structure and the final hydrogen storage properties of the alloys. Extensive absorption/desorption experiments (Van’t Hoff diagrams) have shown that such alloys can be used to build a metal hydride compressor (MHC), compressing H 2 gas from 0.2 MPa to 4.2 MPa using cold (20 °C) and hot (80 °C) water

  20. Dependence of hydrogen storage characteristics of mechanically milled carbon materials on their host structures

    Shindo, K.; Kondo, T.; Sakurai, Y.

    2004-01-01

    We investigated whether the hydrogen storage characteristics of carbon materials prepared by mechanical milling in an H 2 atmosphere were dependent on their host structures. We used natural graphite (NG) and activated carbon fibers (ACF) and compared them with activated carbon (AC) powders. The XRD patterns of NG and ACF milled for over 20 h and SEM images of these samples milled for 80 h were almost the same as those of AC. The hydrogen storage capacities of NG and ACF estimated by the inert gas fusion-thermal conductivity method increased with the mechanical milling time up to 10 h and showed little milling time dependence thereafter. The capacities of NG and ACF reached about 3.0 wt.% and were similar to that of AC. However, it should be noted that the hydrogen storage mechanism of NG and ACF mechanically milled in an H 2 atmosphere might be different because the changes in their specific surface areas with milling time were opposite. Thermal desorption mass spectroscopy (TDS) revealed that the desorption spectra of the hydrogen molecules (mass number=2) of NG and ACF milled for 10 h in the same way as AC contained two peaks at about 500 and 800 deg. C. The desorption activation energies of hydrogenated NG and ACF at these peaks calculated from a Kissinger plot were almost with the same as those of hydrogenated AC. This suggests that the state of the hydrogen trapped in the structural defects in NG introduced by the mechanical milling may be almost the same as that of AC. In addition, we assumed the possibility that the state of the hydrogen in ACF hydrogenated by mechanical milling could be almost the same as that in hydrogenated AC. We considered that the nanocarbon materials hydrogenated under our milling conditions had very similar physical shapes and hydrogen storage capacities, independent of their host structures

  1. The laser desorption/laser ionization mass spectra of some methylated xanthines and the laser desorption of caffeine and theophylline from thin layer chromatography plates

    Rogers, Kevin; Milnes, John; Gormally, John

    1993-02-01

    Laser desorption/laser ionization time-of-flight mass spectra of caffeine, theophylline, theobromine and xanthine are reported. These mass spectra are compared with published spectra obtained using electron impact ionization. Mass spectra of caffeine and theophylline obtained by IR laser desorption from thin layer chromatography plates are also described. The laser desorption of materials from thin layer chromatography plates is discussed.

  2. Adsorption and desorption of radioactive inert gases in various materials

    Butkus, D.

    1999-01-01

    Peculiarities of the 85 Kr and 133 Xe adsorption and desorption processes in active carbon and paraffin are considered in the work. During the desorption process, the distribution of 85 Kr and 133 Xe atoms in active carbon particles is uneven: atoms in narrow micropores desorb the last. It is shown that by changing adsorption conditions the presence time of radioactive inert gases in an active carbon can be prolonged. The adsorption and desorption processes change in the adsorbent, which changes its aggregation state: adsorption occurs in a liquid absorbent and desorption - in a solid absorbent. Paraffin is just such an absorbent changing its aggregation state with low energy losses. It has been obtained that 133 Xe accumulates less in liquid paraffin that in an active carbon. The absorption of 85 Kr in paraffin is larger than in an active carbon (at 18-20 degrees Celsius), while desorption is slower. The velocity of radioactive inert gas atom motion in different places of a solid paraffin sample is different - it increases approaching the borders of the sample. Prolongation of the desorption time of radioactive inert gases from adsorbents and adsorbents in many cases is of a practical importance. In this work, it has been shown by model experiments that the intensity of adsorption and desorption processes for the same sorbents can be changed. Desorption intensity changes are related to the distribution of gas atoms on the surface of particles and in micropores. Desorption velocity decreases if inert gas atoms having entered micropores are 'closed' by condensed liquids in the environment. In this case an inert gas atom diffuses within the whole particle volume or through the condensed liquid. Radioactive inert gases 85 Kr and 133 Xe are absorbed not only in liquid paraffin but in solid one as well. Therefore, after a paraffin sample is hermetically closed in a glass dish, 85 Kr (gas) having diffused from this sample is repeatedly absorbed in it. The 85 Kr

  3. Role of water in the dynamic disproportionation of Zn-based TCNQ(F4) coordination polymers (TCNQ = tetracyanoquinodimethane).

    Nafady, Ayman; Le, Thanh Hai; Vo, Nguyen; Haworth, Naomi L; Bond, Alan M; Martin, Lisandra L

    2014-02-17

    Intriguingly, coordination polymers containing TCNQ(2–) and TCNQF4(2–) (TCNQ = 7,7,8,8-tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, both designated as TCNQ(F4)(2–)) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN(2–) revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN(2+). Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– TCNQ(F4)MeCN + TCNQ(F4)MeCN(2–) is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10(–10); TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN(2+) + 2 TCNQ(F4)MeCN•– ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble ZnTCNQ(F4)(s) and the loss of TCNQ(F4)MeCN•– were verified by UV–visible and infrared spectroscopy and steady-state voltammetry. Importantly, the reverse reaction of comproportionation rather than disproportionation becomes the favored process in the presence of ≥3% (v/v) water, due to the increased solubility of solid ZnTCNQ(F4)(s). Thus, in this “wet” environment, ZnMeCN(2+) and TCNQ(F4)MeCN•– are produced from a mixture of ZnTCNQ(F4)(s) and TCNQ(F4)MeCN and with the addition of water provides a medium for synthesis of [Zn(TCNQ(F4))2(H2O)2]. An important conclusion from this work is that the redox level of TCNQ(F4)-based materials, synthesized from a mixture of metal cations and TCNQ(F4)•–, is controlled by a solvent-dependent disproportionation/comproportionation reaction that may be tuned to favor formation of solids containing the monoanion radical, the dianion, or even a mixture of both.

  4. Sorption-desorption behavior of polybrominated diphenyl ethers in soils

    Olshansky, Yaniv; Polubesova, Tamara; Vetter, Walter; Chefetz, Benny

    2011-01-01

    Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4'-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K OC ) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration. - Highlights: → BDE-15 exhibited pronounced desorption hysteresis. → BDE-15 sowed higher sorption affinity to humin as compared to the bulk soils. → Sequestration of PBDEs depends on soil organic matter constitutes other than humin. - Pronounced desorption hysteresis was observed for BDE-15 in natural soils.

  5. Desorption of absorbed iron in bean root and leaf tissues

    Jooste, J.H.; De Bruyn, J.A.

    1979-01-01

    The effect of different desorption media on the amount of absorbed Fe (from a solution of FeCl 3 in 0,5 mM CaCl 2 ) retained by leaf discs and excised root tips of bean plants was investigated. Attempts were also made to determine the effect of desorption on the intracellular distribution of Fe. Desorption in water or an FeCl 3 solution had no pronounced effect on the amount of absorbed Fe retained by either the leaf or root tissues. However, Na 2 -EDTA was able to desorb a considerable portion of the absorbed Fe, especially in root tissue. This applies to Fe absorbed from solutions of FeCl 3 and Fe-EDDHA. Desorption by the chelate removed Fe from practically all the different particulate fractions of both root and leaf tissues, but desorption following the longer absorption periods resulted in an increase in the Fe content of the 'soluble' fraction. The possibility that Na 2 -EDTA causes an increased permeability of cell membranes seems likely. The view that removal of Ca by the chelate causes this increase in permeability could not be confirmed [af

  6. Influence of surface coverage on the chemical desorption process

    Minissale, M.; Dulieu, F., E-mail: francois.dulieu@obspm.fr [LERMA, Université de Cergy Pontoise et Observatoire de Paris, UMR 8112 du CNRS. 5, mail Gay Lussac, 95031 Cergy Pontoise (France)

    2014-07-07

    In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorption efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.

  7. Sorption-desorption dynamics of radiocaesium in organic matter soils

    Valcke, E.; Cremers, A.

    1994-01-01

    A systematic study has been carried out on the radiocaesium sorption properties of 25 soils (forest, peat) covering organic matter (OM) contents in the range of 10-97%. Predictions are made for radiocaesium partitioning between micaceous Frayed Edge Sites (FES) and regular exchange sites (RES) on the basis of specific radiocaesium interception potentials of the soil and overall exchange capacity. It is shown that for soils with a very high OM content (>80%), significant fractions are present in a readily reversible form in the OM phase. In soils of low-medium OM content (<40%), only a very minor fraction is present in the OM exchange complex. Experimental findings, based on a desorption screening with a variety of desorption agents are in agreement with these predictions. On the basis of a study of sorption kinetics, some additional tools are available for identifying problem soils. In cases of very high OM content, radiocaesium adsorption is completed within hours demonstrating the involvement of the OM sites. In soils for which interception occurs in the FES, sorption continues to proceed for periods of 2-3 weeks. In conclusion, some examples are presented on radiocaesium desorption using ion exchangers as radiocaesium sinks in promoting desorption. For a peaty soil, near quantitative desorption is accomplished. For forest soils with OM contents in a range of 10-40%, fixation levels of 30-50% are demonstrated

  8. Hydrogen adsorption on bimetallic PdAu(111) surface alloys

    Takehiro, Naoki; Liu, Ping; Bergbreiter, Andreas

    2014-01-01

    The adsorption of hydrogen on structurally well defined PdAu-Pd(111) monolayer surface alloys was investigated in a combined experimental and theoretical study, aiming at a quantitative understanding of the adsorption and desorption properties of individual PdAu nanostructures. Combining...... the structural information obtained by high resolution scanning tunneling microscopy (STM), in particular on the abundance of specific adsorption ensembles at different Pd surface concentrations, with information on the adsorption properties derived from temperature programmed desorption (TPD) spectroscopy...... and high resolution electron energy loss spectroscopy (HREELS) provides conclusions on the minimum ensemble size for dissociative adsorption of hydrogen and on the adsorption energies on different sites active for adsorption. Density functional theory (DFT) based calculations give detailed insight...

  9. The Inverse Problem of Identification of Hydrogen Permeability Model

    Yury V. Zaika

    2018-01-01

    Full Text Available One of the technological challenges for hydrogen materials science is the currently active search for structural materials with important applications (including the ITER project and gas-separation plants. One had to estimate the parameters of diffusion and sorption to numerically model the different scenarios and experimental conditions of the material usage (including extreme ones. The article presents boundary value problems of hydrogen permeability and thermal desorption with dynamical boundary conditions. A numerical method is developed for TDS spectrum simulation, where only integration of a nonlinear system of low order ordinary differential equations is required. The main final output of the article is a noise-resistant algorithm for solving the inverse problem of parametric identification for the aggregated experiment where desorption and diffusion are dynamically interrelated (without the artificial division of studies into the diffusion limited regime (DLR and the surface limited regime (SLR.

  10. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  11. Mechanistic study of the isotopic-exchange reaction between gaseous hydrogen and palladium hydride powder

    Outka, D.A.; Foltz, G.W.

    1991-01-01

    A detailed mechanism for the isotopic-exchange reaction between gaseous hydrogen and solid palladium hydride is developed which extends previous model for this reaction by specifically including surface reactions. The modeling indicates that there are two surface-related processes that contribute to the overall rate of exchange: the desorption of hydrogen from the surface and the exchange between surface hydrogen and bulk hydrogen. This conclusion is based upon measurements examining the effect of small concentrations of carbon monoxide were helpful in elucidating the mechanism. Carbon monoxide reversibly inhibits certain steps in the exchange; this slows the overall rate of exchange and changes the distribution of products from the reactor

  12. Metastable hydrogen

    Dose, V.

    1982-01-01

    This paper deals with the basic physical properties of the metastable 2 2 sub(1/2) state of atomic hydrogen. Applications relying on its special properties, including measurement of the Lamb shift, production of spin-polarized protons and the measurement of molecular electric moments, are discussed. (author)

  13. Hydrogen storage study on Ti2CrV and ZrFe1.8V0.2 composite system

    Banerjee, S.; Kumar, A.; Pillai, C.G.S.; Sudarsan, V.

    2012-01-01

    Ti 2 CrV is reported to have one of the highest hydrogen storage capacities (more than 4 wt. %) among the bcc phase transition metal alloys. It has been found from the earlier study that Ti 2 CrV alloy shows quite good hydrogen absorption property but the desorption temperature is on the higher side. The in-situ temperature programmed desorption profile shows that the hydrogen desorption starts from 120℃ and the desorption peak comes at 180℃, which is slightly high for the vehicular application. On the other hand ZrFe 1.8 V 0.2 Laves phase alloy has low hydrogen absorption capacity, but at the room temperature it can desorp all its hydrogen. The pressure composition isotherm of ZrFe 1.8 V 0.2 alloy generated during the experiment shows the typical characteristics of the room temperature reversible hydride. The in-situ temperature programmed desorption shows that the hydride can desorb all the hydrogen below room temperature

  14. Data compilation for radiation effects on hydrogen recycle in fusion reactor materials

    Ozawa, Kunio; Fukushima, Kimichika; Ebisawa, Katsuyuki.

    1984-05-01

    Irradiation tests of materials by hydrogen isotopes are under way, to investigate the hydrogen recycling process where exchange of fuel particles takes place between plasma and the wall of the nuclear fusion reactor. In the report, data on hydrogen irradiation are collected and reviewed from the view point of irradiation effects. Data are classified into, (1) Re-emmission, (2) Retention, (Retained hydrogen isotopes, Depth profile in the materials and Thermal desorption spectroscopy), (3) Permeation and (4) Ion impact desorption. Research activities in each area are arranged according to the date of publication, research institutes, materials investigated, so that overview of present status can be made. Then, institute, author and reference are shown for each classification with tables. The list of literature is also attached. (author)

  15. Recyclable hydrogen storage system composed of ammonia and alkali metal hydride

    Yamamoto, Hikaru [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Miyaoka, Hiroki; Hino, Satoshi [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Nakanishi, Haruyuki [Higashi-Fuji Technical Center, Toyota Motor Corporation, 1200 Misyuku, Susono, Shizuoka 410-1193 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan)

    2009-12-15

    Ammonia (NH{sub 3}) reacts with alkali metal hydrides MH (M = Li, Na, and K) in an exothermic reaction to release hydrogen (H{sub 2}) at room temperature, resulting that alkali metal amides (MNH{sub 2}) which are formed as by-products. In this work, hydrogen desorption properties of these systems and the condition for the recycle from MNH{sub 2} back to MH were investigated systematically. For the hydrogen desorption reaction, the reactivities of MH with NH{sub 3} were better following the atomic number of M on the periodic table, Li < Na < K. It was confirmed that the hydrogen absorption reaction of all the systems proceeded under 0.5 MPa of H{sub 2} flow condition below 300 C. (author)

  16. Industrial implications of hydrogen

    Pressouyre, G.M.

    1982-01-01

    Two major industrial implications of hydrogen are examined: problems related to the effect of hydrogen on materials properties (hydrogen embrittlement), and problems related to the use and production of hydrogen as a future energy vector [fr

  17. Hydrogen isotope effect on storage behavior of U{sub 2}Ti and UZr{sub 2.3}

    Jat, Ram Avtar; Sawant, S.G.; Rajan, M.B.; Dhanuskar, J.R. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Kaity, Santu [Radiometallurgy Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Parida, S.C., E-mail: sureshp@barc.gov.in [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2013-11-15

    U{sub 2}Ti and UZr{sub 2.3} alloys were prepared by arc melting method, vacuum annealed and characterized by XRD, SEM and EDX methods. Hydrogen isotope effect on the storage behavior of these alloys were studied by measuring the hydrogen/deuterium desorption pressure–composition–temperature (PCT) profiles in the temperature range of 573–678 K using a Sievert’s type volumetric apparatus. It was observed that, in the temperature and pressure range of investigation, all the isotherms show a single desorption plateau. The PCT data reveals that both U{sub 2}Ti and UZr{sub 2.3} alloys had normal isotope effects on hydrogen/deuterium desorption at all experimental temperatures. Thermodynamic parameters for dehydrogenation and dedeuteration reactions of the corresponding hydrides and deuterides of the above alloys were deduced from the PCT data.

  18. Study of defects near molybdenum surface using thermal desorption spectrometer

    Naik, P.K.

    1980-01-01

    Thermal desorption spectrometry is utilized to study the migration of atoms and defects near molybdenum surface. The thermal desorption spectra of inert gas ions (neon, argon and krypton) injected with various energies (430-1950 eV) into a polycrystalline molybdenum target with various dosages (6.4 x 10sup(12) - 3.9 x 10sup(14) ions/cmsup(2)) are investigated. Four different states of binding of the trapped atoms corresponding to the activation energies for desorption have been revealed from the spectra. The activation energies are found to be relatively insensitive to the species of the bombarding ion, incident ion energy and the dosage. The patterns of the spectra are strongly influenced by the mean projected range of the ions into the solid. The activation energies deduced are in good agreement with those reported for the migration of atoms and defects in molybdenum. (auth.)

  19. A study of the process of desorption of hexavalent chromium

    W.B. Amorim

    2003-09-01

    Full Text Available In this work the process of desorption of hexavalent chromium, a toxic metal ion, from the marine algae Sargassum sp, following biosorption experiments 2³ factorial design was studied. A technique was applied to three eluents: HCl, H2SO4 and EDTA. Three factors of importance were evaluated: concentration of eluent, the ratio between mass of biosorbent and volume of eluent (S/L and process time. A statistical analysis of the experimental results showed that the three variables evaluated are significant for all three eluents. The models for chromium desorption were validated, as the results agreed well with the observed values. Through use of the response surface methodology, a factorial design based optimization technique; it was possible to identify the most suitable eluent and the interval of values for the process variables that resulted in the most significant desorption of chromium, which is relevant information for work aiming at process optimization.

  20. Study of the mechanisms of matrix assisted laser desorption / ionization

    Manuelli, Pascal

    1995-01-01

    This research thesis aims at a better knowledge of some aspects of a complex mechanism: the matrix-assisted laser desorption/ionization (MALDI). The author first proposes a comparative analysis of results obtained by time-of-flight (TOF) mass spectrometry and by Fourier transform mass spectrometry. He reports the study of the matrix role (notably a polymeric matrix) as a matter submitted to laser desorption. In this respect, the influence of the incident wavelength has been studied. The author also reports a comparative of ions produced by matrix laser desorption (study performed by Fourier transform mass spectrometry) and of neutral molecules (study performed by flash pyrolysis coupled with gas chromatography and with mass spectrometry). Finally, results obtained on derivatives and complexes based on beta-cyclodextrins highlight benefits as well as limitations of this technique [fr

  1. Electron stimulated desorption of gases at technological surfaces of aluminium

    Ding, M.Q.; Williams, E.M.

    1989-01-01

    The release of gas by electron bombardment at aluminium alloy surfaces in vacuum -9 torr has been investigated for a range of treatments including bakeout and glow discharge cleaning. Particular attention has been given to the role of continuous electron bombardment, with current densities and electron energies of up to 1.5 mA cm -2 and 2.0 keV, respectively, over the 10 cm 2 of surface area under irradiation. The observations of desorption efficiency, defined as the number of desorbed molecules per incident electron, conform to a model involving a dynamic balance between adsorption and desorption, with contributions to adsorption from both surface and sub-surface gas. Continuous electron bombardment promotes a surface with low desorption efficiency, -5 mol/electron, however, the conditioning cycle is accelerated significantly by glow discharge treatment. There is evidence of some short-term memory when the samples are exposed to air. (author)

  2. Coverage dependent desorption dynamics of deuterium on Si(100) surfaces: interpretation with a diffusion-promoted desorption model.

    Matsuno, T; Niida, T; Tsurumaki, H; Namiki, A

    2005-01-08

    We studied coverage dependence of time-of-flight (TOF) spectra of D2 molecules thermally desorbed from the D/Si(100) surface. The mean translational energies Et of desorbed D2 molecules were found to increase from 0.20+/-0.05 eV to 0.40+/-0.04 eV as the desorption coverage window was decreased from 1.0 ML> or =thetaD> or =0.9 ML to 0.2 ML> or =thetaD> or =0 ML, being consistent with the kinetics switch predicted in the interdimer mechanism. The measured TOF spectra were deconvoluted into 2H, 3H, and 4H components by a curve fitting method along the principle of detailed balance. As a result, it turned out that the desorption kinetics changes from the 4H to the 3H situation at high coverage above thetaD=0.9 ML, while the 2H desorption is dominant for a quite wide coverage region up to thetaD=0.8 ML. A dynamic desorption mechanism by which the desorption is promoted by D-atom diffusion to dangling bonds was proposed. 2005 American Institute of Physics.

  3. Corrosion and hydrogen absorption of commercially pure zirconium in acid fluoride solutions

    Yokoyama, Ken’ichi; Yamada, Daisuke; Sakai, Jun’ichi

    2013-01-01

    Highlights: •Zirconium corrodes and absorbs hydrogen in acid fluoride solutions. •Hydrogen thermal desorption is observed at 300–700 °C. •The resistance to hydrogen absorption of zirconium is higher than that of titanium. -- Abstract: The corrosion and hydrogen absorption of commercially pure zirconium have been investigated in acidulated phosphate fluoride (APF) solutions. Upon immersion in 2.0% APF solution of pH 5.0 at 25 °C, a granular corrosion product (Na 3 ZrF 7 ) deposits over the entire side surface of the specimen, thereby inhibiting further corrosion. In 0.2% APF solution, marked corrosion is observed from the early stage of immersion; no deposition of the corrosion product is observed by scanning electron microscopy. A substantial amount of hydrogen absorption is confirmed in both APF solutions by hydrogen thermal desorption analysis. The amount of absorbed hydrogen of the specimen immersed in the 2.0% APF solution is smaller than that in the 0.2% APF solution in the early stage of immersion. The hydrogen absorption behavior is not always consistent with the corrosion behavior. Hydrogen thermal desorption occurs in the temperature range of 300–700 °C for the specimen without the corrosion product. Under the same immersion conditions, the amount of absorbed hydrogen in commercially pure zirconium is smaller than that in commercially pure titanium as reported previously. The present results suggest that commercially pure zirconium, compared with commercially pure titanium, is highly resistant to hydrogen absorption, although corrosion occurs in fluoride solutions

  4. Long-term desorption of trichloroethylene from flint clay using multiplexed optical detection

    Stager, M.P.; Perram, G.P.

    1999-01-01

    The long-term desorption of trichloroethylene (TCE) from powdered flint clay was examined using a multiplexed, phase sensitive infrared technique which provided a gas phase detection limit of 0.0045 torr for continuous monitoring of the desorption process for at least 3 days. The vapor phase TCE concentrations as a function of desorption time exhibit a significant deviation from Langmuir kinetics. The desorption process is adequately described by bonding sites with a gamma distribution for the desorption rate coefficients. The mean desorption rate for powdered flint clay at 25°C is k d = 0.50 ± 0.02 h −1 . (author)

  5. Modelling of Convective Process of Water Desorption from Polystyrene

    Stakic, M.; Nikolic, A.

    2008-01-01

    This study presents a mathematical model developed to evaluate the influence of structural and operational factors on convective dehydration process (desorption of liquid phase from capillary-porous material), as well as the possibility to utilize this model for the case of water desorption from polystyrene cation resin CG-8. The model accounts for unsteady one-dimensional simultaneous heat and mass transfer between the gas (air) and the solid phase (resin). The identification of effective transport properties for the considered fixed bed of material (resin CG 8) is discussed. To this purpose available data from the literature are used. (author)

  6. Sorption and desorption of diuron in Oxisol under biochar application

    Petter,Fabiano André; Ferreira,Tamara Santos; Sinhorin,Adilson Paulo; Lima,Larissa Borges de; Morais,Leidimar Alves de; Pacheco,Leandro Pereira

    2016-01-01

    ABSTRACT The objective of this study was to verify the kinetics of sorption and desorption of diuron in an Oxisol under application of biochar. The samples were collected in a field experiment conducted in randomized design blocks consisted of 2 base fertilization levels (0 and 400 kg∙ha−1 NPK 00-20-20 fertilizer formula) and 3 doses of biochar (0, 8 and 16 Mg∙ha−1). In the evaluation of sorption and desorption, Batch Equilibrium method was used. The kinetics of sorpti...

  7. Counterion adsorption and desorption rate of a charged macromolecule

    Shi, Yu; Yang, Jingfa; Zhao, Jiang

    The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

  8. Heavy-Ion-Induced Electronic Desorption of Gas from Metals

    Molvik, A W; Mahner, E; Kireeff Covo, M; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Krämer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2007-01-01

    During heavy-ion operation in several particle accelerators worldwide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion-induced gas desorption scales with the electronic energy loss (dEe/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  9. Bulk-mediated surface diffusion: non-Markovian desorption dynamics

    Revelli, Jorge A; Budde, Carlos E; Prato, Domingo; Wio, Horacio S

    2005-01-01

    Here we analyse the dynamics of adsorbed molecules within the bulk-mediated surface diffusion framework, when the particle's desorption mechanism is characterized by a non-Markovian process, while the particle's adsorption as well as its motion in the bulk is governed by Markovian dynamics. We study the diffusion of particles in both semi-infinite and finite cubic lattices, analysing the conditional probability to find the system on the reference absorptive plane as well as the surface dispersion as functions of time. The results are compared with known Markovian cases showing the differences that can be exploited to distinguish between Markovian and non-Markovian desorption mechanisms in experimental situations

  10. Anomalous low-temperature desorption from preirradiated rare gas solids

    Savchenko, E.V.; Gumenchuk, G.B.; Yurtaeva, E.M.; Belov, A.G.; Khyzhniy, I.V.; Frankowski, M.; Beyer, M.K.; Smith-Gicklhorn, A.M.; Ponomaryov, A.N.; Bondybey, V.E.

    2005-01-01

    The role for the exciton-induced defects in the stimulation of anomalous low-temperature desorption of the own lattice atoms from solid Ar and Ne preirradiated by an electron beam is studied. The free electrons from shallow traps-structural defects-was monitored by the measurements of a yield of the thermally induced exoelectron emission (TSEE). The reaction of recombination of self-trapped holes with electrons is considered as a source of energy needed for the desorption of atoms from the surface of preirradiated solids. A key part of the exciton-induced defects in the phenomenon observed is demonstrated

  11. Study of heterogeneous catalytic processes over cobalt, molybdenum and cobalt-molybdenum catalysts supported on alumina by temperature-programmed desorption and temperature-programmed reaction. 1. Adsorption of hydrozen

    Rozanov, V.V.; Tsao Yamin; Krylov, O.V.

    1996-01-01

    Hydrogen adsorption on reduced, sulphidized and reoxidized specimens of molybdenum-and cobalt-molybdenum-containing catalysts applied on aluminium oxide has been studied by the method of thermal desorption (TD). Comparison of TD spectra of hydrogen and data of X-ray phase analysis of the specimens and mass-spectrometric analysis of the products desorbed from the surface of catalysts after their successive reduction sulphidizing, carbonizing and reoxidation permitted a correlation between various forms of hydrogen adsorption and certain centres on the surface of the catalysts. 12 refs., 2 figs

  12. The kinetic isotope effect of hydrogen, deuterium and tritium absorbed and desorbed by titanium

    Huang Gang; Cao Xiaohua; Long Xinggui

    2008-06-01

    p-t curves of hydrogen, deuterium and tritium absorption at 550-750 degree C and desorption at 350-550 degree C by titanium were investigated. The rate constants of absorption and desorption for hydrogen, deuterium and tritium on each temperature are determined and the activation energy values obtained by this analysis are (55.6 ± 2.4) kJ·mol -1 , (110.2 ± 3.0) kJ·mol -1 and (155.5 ± 3.2) kJ·mol -1 for absorption and (27.1±0.4) KJ·mol -1 , (42.3 ± 1.9) kJ·mol -1 and (62.1±1.6) kJ·mol -1 for desorption respectively. The activation energy value of tritium absorption is highest which shows titanium tritiation is hardest. The activation energy value of tritium desorption is highest and it also can prove that titanium tritide is stablest. There are remarkable kinetic hydrogen isotope effects when titanium absorb and desorb hydrogen, deuterium and tritium. (authors)

  13. Modeling and experimental verification of the thermodynamic properties of hydrogen storage materials

    Ledovskikh, A.V.; Danilov, D.L.; Vliex, M.F.H.; Notten, P.H.L.

    2016-01-01

    A new mathematical model has been developed describing the thermodynamics of the hydrogen absorption and desorption process in Metal Hydrides via the gas phase. This model is based on first principles chemical and statistical thermodynamics and takes into account structural changes occurring inside

  14. Conceptual design of hydrogen isotopes chromatographic separation system with super large capacity

    Xie Bo; Weng Kuiping; Liu Yunnu; Hou Jianping

    2012-01-01

    A super large capacity hydrogen isotopes separation system, including total plan, unit (including making and purification of gas, three-grade chromatographic columns, gas loop and auto-control, and carrier recovery) and experimental scheme, had been designed on the basis of a series of hydrogen-deuterium experiments by temperature programmed de- sorption. The characteristic of the system was that desorption kinetic parameters could be directly calculated from the hydrogen isotope separation desorption spectra information. In other words, the complicated dynamic process of separation could be described by the desorption rate equation, shape parameter and desorption activation energy calculation on the condition of the experimental data and appropriate assumptions (equilibrium and adsorption, uniform surface). In previous work, an experimental series of operation to verify the successive enrichment of D 2 from a H 2 -D 2 mixture, the production of the deuterium from natural hydrogen and the recovery of tritium such as from the nuclear heavy-water were carried out using MS5A at 77 K. This work was only conceptual design, so it was necessary to identify the availability of super large capacity system by experiment. (authors)

  15. Density Functional Theory Study of the Interaction of Hydrogen with Li6C60.

    Wang, Qian; Jena, Puru

    2012-05-03

    Hydrogen storage properties of Li-coated C60 fullerene have been studied using density functional theory within the local density as well as generalized gradient approximation. Hydrogen atoms are found to bind to Li6C60 in two distinct forms, with the first set attaching to C atoms, not linked to Li, in atomic form. Once all such C atoms are saturated with hydrogen, the second set of hydrogen atoms bind quasi-molecularly to the Li atoms, five of which remain in the exohedral and the sixth in the endohedral position. The corresponding hydrogen gravimetric density in Li6C60H40 is 5 wt %. Desorption of hydrogen takes place in succession, the ones bound quasi-molecularly desorbing at a temperature lower than the ones bound atomically. The results are compared with the recent experiment on hydrogen adsorption in Li6C60.

  16. Study of ionization process of matrix molecules in matrix-assisted laser desorption ionization

    Murakami, Kazumasa; Sato, Asami; Hashimoto, Kenro; Fujino, Tatsuya, E-mail: fujino@tmu.ac.jp

    2013-06-20

    Highlights: ► Proton transfer and adduction reaction of matrix in MALDI were studied. ► Hydroxyl group forming intramolecular hydrogen bond was related to the ionization. ► Intramolecular proton transfer in the electronic excited state was the initial step. ► Non-volatile analytes stabilized protonated matrix in the ground state. ► A possible mechanism, “analyte support mechanism”, has been proposed. - Abstract: Proton transfer and adduction reaction of matrix molecules in matrix-assisted laser desorption ionization were studied. By using 2,4,6-trihydroxyacetophenone (THAP), 2,5-dihydroxybenzoic acid (DHBA), and their related compounds in which the position of a hydroxyl group is different, it was clarified that a hydroxyl group forming an intramolecular hydrogen bond is related to the ionization of matrix molecules. Intramolecular proton transfer in the electronic excited state of the matrix and subsequent proton adduction from a surrounding solvent to the charge-separated matrix are the initial steps for the ionization of matrix molecules. Nanosecond pump–probe NIR–UV mass spectrometry confirmed that the existence of analyte molecules having large dipole moment in their structures is necessary for the stabilization of [matrix + H]{sup +} in the electronic ground state.

  17. Desorption of protium and deuterium from different types of titanium beds

    Ionete, Eusebiu Ilarian; Dylst, Kris; Gheorghe, Costeanu Claudiu; Stefan, Spiridon Ionut; Florian, Monea Bogdan; Broeckx, Wouter

    2017-01-01

    When the long term tritium storage is intended, metal hydride materials, particularly the titanium (Ti) beds, seems to be the recommended option, due to its compliance with the criteria of selection (e.g. material cost, stability, storage capacity, loading and unloading conditions, or radioactivity). However few experimental and numerical analyses have been published so far to better support the understanding of the recovery capabilities for different forms of titanium beds. In this work, an investigation on the recovery of different hydrogen isotopes from two types of titanium (Ti) beds, namely Ti powder and Ti sponge, has been performed. Hydrogen isotope release was experimentally verified up to a temperature of 600 °C for both Ti powder and Ti sponge beds. The desorption percentages were determined to be from 24.98 to 20.54 in the case of D_2 on Ti sponge, and from 34.36 to 29.77 in the case of H_2 on Ti sponge. The paper describes in detail the experimental set up, the measurements and the drawn conclusions.

  18. Desorption of protium and deuterium from different types of titanium beds

    Ionete, Eusebiu Ilarian, E-mail: eusebiu.ionete@icsi.ro [National Research and Development Institute for Cryogenics and Isotopic Technologies—ICSI Rm. Valcea, 240050 Ramnicu Valcea (Romania); Dylst, Kris [SCK-CEN, Boeretang 200, 2400 Mol (Belgium); Gheorghe, Costeanu Claudiu; Stefan, Spiridon Ionut; Florian, Monea Bogdan [National Research and Development Institute for Cryogenics and Isotopic Technologies—ICSI Rm. Valcea, 240050 Ramnicu Valcea (Romania); Broeckx, Wouter [SCK-CEN, Boeretang 200, 2400 Mol (Belgium)

    2017-03-15

    When the long term tritium storage is intended, metal hydride materials, particularly the titanium (Ti) beds, seems to be the recommended option, due to its compliance with the criteria of selection (e.g. material cost, stability, storage capacity, loading and unloading conditions, or radioactivity). However few experimental and numerical analyses have been published so far to better support the understanding of the recovery capabilities for different forms of titanium beds. In this work, an investigation on the recovery of different hydrogen isotopes from two types of titanium (Ti) beds, namely Ti powder and Ti sponge, has been performed. Hydrogen isotope release was experimentally verified up to a temperature of 600 °C for both Ti powder and Ti sponge beds. The desorption percentages were determined to be from 24.98 to 20.54 in the case of D{sub 2} on Ti sponge, and from 34.36 to 29.77 in the case of H{sub 2} on Ti sponge. The paper describes in detail the experimental set up, the measurements and the drawn conclusions.

  19. Thermogravimetric research of hydrogen storage materials

    Kleperis, J; Grinberga, L; Ergle, M; Chikvaidze, G; Klavins, J

    2007-01-01

    During thermogravimetric research of metal hydrides we noticed mass growth of samples above 200 deg. C even in an argon atmosphere. Further heating is leading to the growth of weight up to 2-7 weight% till 500 0 C. Second run of the same sample without taking out of DTA instrument gave only small mass changes, indicating that noticed mass increase during first run is permanent. Microscope and elemental analyses were made to determine the reason of mass growth. XRD inspection revealed the formation of new phase with bunsenite NiO structure with deformed cubic structure. The new phase is no more active to hydrogen sorption/desorption. Our results demonstrated that the usage of hydrogen storage alloys AB 5 must be taken with care - it is important not to exceed some critical temperature were irreversible structural, compositional and morphological changes will occur

  20. A comparison of hydrogen vs. helium glow discharge effects on fusion device first-wall conditioning

    Dylla, H.F.

    1989-09-01

    Hydrogen- and deuterium-fueled glow discharges are used for the initial conditioning of magnetic fusion device vacuum vessels following evacuation from atmospheric pressure. Hydrogenic glow discharge conditioning (GDC) significantly reduces the near-surface concentration of simple adsorbates, such as H 2 O, CO, and CH 4 , and lowers ion-induced desorption coefficients by typically three orders of magnitude. The time evolution of the residual gas production observed during hydrogen-glow discharge conditioning of the carbon first-wall structure of the TFTR device is similar to the time evolution observed during hydrogen GDC of the initial first-wall configuration in TFTR, which was primarily stainless steel. Recently, helium GDC has been investigated for several wall-conditioning tasks on a number of tokamaks including TFTR. Helium GDC shows negligible impurity removal with stainless steel walls. For impurity conditioning with carbon walls, helium GDC shows significant desorption of H 2 O, CO, and CO 2 ; however, the total desorption yield is limited to the monolayer range. In addition, helium GDC can be used to displace hydrogen isotopes from the near-surface region of carbon first-walls in order to lower hydrogenic retention and recycling. 38 refs., 6 figs

  1. Ice XVII as a Novel Material for Hydrogen Storage

    Leonardo del Rosso

    2017-02-01

    Full Text Available Hydrogen storage is one of the most addressed issues in the green-economy field. The latest-discovered form of ice (XVII, obtained by application of an annealing treatment to a H 2 -filled ice sample in the C 0 -phase, could be inserted in the energy-storage context due to its surprising capacity of hydrogen physisorption, when exposed to even modest pressure (few mbars at temperature below 40 K, and desorption, when a thermal treatment is applied. In this work, we investigate quantitatively the adsorption properties of this simple material by means of spectroscopic and volumetric data, deriving its gravimetric and volumetric capacities as a function of the thermodynamic parameters, and calculating the usable capacity in isothermal conditions. The comparison of ice XVII with materials with a similar mechanism of hydrogen adsorption like metal-organic frameworks shows interesting performances of ice XVII in terms of hydrogen content, operating temperature and kinetics of adsorption-desorption. Any application of this material to realistic hydrogen tanks should take into account the thermodynamic limit of metastability of ice XVII, i.e., temperatures below about 130 K.

  2. Kinetic and Mechanistic Aspects of the Reactions of Iodide and Hypoiodous Acid with Permanganate: Oxidation and Disproportionation.

    Zhao, Xiaodan; Salhi, Elisabeth; Liu, Huiling; Ma, Jun; von Gunten, Urs

    2016-04-19

    Oxidation kinetics of iodide and HOI/OI(-) by permanganate were studied in the pH range of 5.0-10.0. Iodide oxidation and iodate formation were faster at lower pH. The apparent second-order rate constants (k(obs)) for iodide oxidation by permanganate decrease with increasing pH from 29 M(-1) s(-1) at pH 5.0 and 6.9 M(-1) s(-1) at pH 7.0 to 2.7 M(-1) s(-1) at pH 10.0. k(obs) for HOI abatement are 56 M(-1) s(-1) at pH 5.0, 2.5 M(-1) s(-1) at pH 7.0, and 173 M(-1) s(-1) at pH 10.0. Iodate yields over HOI abatement decrease from 98% at pH 6.0 to 33% for pH ≥ 9.5, demonstrating that HOI disproportionation dominates HOI transformation by permanganate at pH ≥ 8.0. MnO2 formed as a product from permanganate reduction, oxidizes HOI to iodate for pH oxidation or disproportionation induced by MnO2 is much lower than for permanganate. During treatment of iodide-containing waters, the potential for iodinated disinfection byproducts (I-DBPs) formation is highest at pH 7.0-8.0 due to the long lifetime of HOI. For pH oxidized by permanganate to iodate, whereas for pH ≥ 8.0, HOI/OI(-) undergoes a fast permanganate-mediated disproportionation.

  3. The kinetics of hydrogen removal from liquid sodium

    Gwyther, J.R.; Whittingham, A.C.

    1981-01-01

    The rates of hydrogen removal from liquid sodium-sodium hydride mixtures have been measured as a function of sodium stirring rate at temperatures up to 420 0 C. Two techniques have been employed - removal under continuous evacuation in which hydrogen flow rates were measured using a capillary flow technique and by argon purging in which hydrogen concentrations in the argon carrier gas were measured by gas chromatography. The results have been used to assess the feasibility of thermal decomposition of sodium hydride for the regeneration of hydride-laden LMFBR cold traps. Studies on the kinetics of desorption of hydrogen from solution in liquid sodium at temperatures up to 400 0 C are also presented and possible kinetic mechanisms discussed. (orig.)

  4. Research on hydrogen storage alloys and their uses

    Alcock, C.B.; Hewitt, J.S.; Khatamian, D.; Manchester, F.D.; McLean, A.; Ward, C.A.; Weatherly, G.C.

    1984-01-01

    A brief account is given of the work being done by members of the Centre on the development of hydrogen storage alloys having useful, reliable, and predictable, performance characteristics. Metals and alloys which have been studied, in one or more aspects, so far, include FeTi, and also FeTi with small added amounts of C, Mn, Al and Mischmetal. Experimental work on the FeTi family of alloys has been concentrated on surface structure and surface behaviour and the importance of these for determining successful activation for hydrogen absorption. As a part of development work on control devices responding to temperature changes through hydrogen desorption, experiments have been performed on hydrides of Nb, La-Ni-Al and Ca-Ni. Some theoretical modelling on kinetics of hydrogen absorption into metals has also been done

  5. Electrochemical Hydrogen Storage in a Highly Ordered Mesoporous Carbon

    Dan eLiu

    2014-10-01

    Full Text Available A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

  6. The role of radiation damage on retention and temperature intervals of helium and hydrogen detrapping in structural materials

    Tolstolutskaya, G.D., E-mail: g.d.t@kipt.kharkov.ua [National Science Center “Kharkov Institute of Physics and Technology”, 1, Akademicheskaya St., 61108 Kharkov (Ukraine); Ruzhytskyi, V.V.; Voyevodin, V.N.; Kopanets, I.E.; Karpov, S.A.; Nikitin, A.V. [National Science Center “Kharkov Institute of Physics and Technology”, 1, Akademicheskaya St., 61108 Kharkov (Ukraine)

    2013-11-15

    An experimental study of hydrogen/deuterium behavior in ferritic–martensitic stainless steels EP-450 (Cr13Mo2NbVB), EP-852 (Cr13Mo2VS), and RUSFER-EK-181 (Fe12Cr2WVTaB) is presented. The effect of displacement damage (dpa) resulting from irradiation with helium, hydrogen, and argon ions on features of deuterium detrapping and retention in steels was studied using ion implantation, nuclear reaction depth profiling, and thermal desorption spectrometry techniques. Numerical simulation on the basis of the continuum rate theory was applied for obtaining thermodynamic parameters of deuterium trapping and desorption in steels.

  7. Influence of Surface Charge/Potential of a Gold Electrode on the Adsorptive/Desorptive Behaviour of Fibrinogen

    Dargahi, Mahdi; Konkov, Evgeny; Omanovic, Sasha

    2015-01-01

    Highlights: • Adsorptive/desorptive behavior of fibrinogen (FG) on an electrochemically-polarized gold substrate is reported. • The adsorption affinity of FG (afFG) is constant on a negatively-charged substrate surface. • The afFG increases linearly with an increase in positive substrate surface charge. • The FG adsorption kinetics is strongly dependant on substrate surface charge. • The adsorbed FG layer can be desorbed by electrochemical evolution of hydrogen and oxygen. - Abstract: The effect of gold substrate surface charge (potential) on adsorptive/desorptive behaviour of fibrinogen (FG) was studied by employing differential capacitance (DC) and polarization modulated infrared reflection absorption spectroscopy (PM-IRRAS), in terms of FG adsorption thermodynamics, kinetics, and desorption kinetics. The gold substrate surface charge was modulated in-situ within the electrochemical double-layer region by means of electrochemical potentiostatic polarization in a FG-containing electrolyte, thus avoiding the interference of other physico-chemical properties of the gold surface on FG’s interfacial behaviour. The FG adsorption equilibrium was modeled using the Langmuir isotherm. Highly negative values of apparent Gibbs free energy of adsorption (ranging from from −52.1 ± 0.4 to −55.8 ± 0.8 kJ mol −1 , depending on the FG adsorption potential) indicated a highly spontaneous and strong adsorption of FG onto the gold surface. The apparent Gibbs free energy of adsorption was found to be independent of surface charge when the surface was negatively charged. However, when the gold surface was positively charged, the apparent Gibbs free energy of adsorption exhibited a pronounced linear relationship with the surface charge, shifting to more negative values with an increase in positive electrode potential. The adsorption kinetics of FG was also found to be dependent on gold surface charge in a similar manner to the apparent Gibbs free energy of adsorption

  8. Stable Isotope Systematics of Coalbed Gas during Desorption and Production

    Martin Niemann

    2017-06-01

    Full Text Available The stable carbon isotope ratios of coalbed methane (CBM demonstrate diagnostic changes that systematically vary with production and desorption times. These shifts can provide decisive, predictive information on the behaviour and potential performance of CBM operations. Samples from producing CBM wells show a general depletion in 13C-methane with increasing production times and corresponding shifts in δ13C-CH4 up to 35.8‰. Samples from canister desorption experiments show mostly enrichment in 13C for methane with increasing desorption time and isotope shifts of up to 43.4‰. Also, 13C-depletion was observed in some samples with isotope shifts of up to 32.1‰. Overall, the magnitudes of the observed isotope shifts vary considerably between different sample sets, but also within samples from the same source. The δ13C-CH4 values do not have the anticipated signature of methane generated from coal. This indicates that secondary processes, including desorption and diffusion, can influence the values. It is also challenging to deconvolute these various secondary processes because their molecular and isotope effects can have similar directions and/or magnitudes. In some instances, significant alteration of CBM gases has to be considered as a combination of secondary alteration effects.

  9. Solid Waste Decontamination by Thermal Desorption and Catalytic Oxidation Methods

    Šolcová, Olga; Topka, Pavel; Soukup, Karel; Jirátová, Květa; Váňová, H.; Kaštánek, František

    2014-01-01

    Roč. 68, č. 9 (2014), s. 1279-1282 ISSN 0366-6352 R&D Projects: GA MPO FR-TI1/059 Institutional support: RVO:67985858 Keywords : thermal desorption * catalytic oxidation * soil decontamination Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.468, year: 2014

  10. Bacterial desorption from food container and food processing surfaces.

    McEldowney, S; Fletcher, M

    1988-03-01

    The desorption ofStaphylococcus aureus, Acinetobacter calcoaceticus, and a coryneform from the surfaces of materials used for manufacturing food containers (glass, tin plate, and polypropylene) or postprocess canning factory conveyor belts (stainless steel and nylon) was investigated. The effect of time, pH, temperature, and adsorbed organic layers on desorption was studied.S. aureus did not detach from the substrata at any pH investigated (between pH 5 and 9).A. calcoaceticus and the coryneform in some cases detached, depending upon pH and substratum composition. The degree of bacterial detachment from the substrata was not related to bacterial respiration at experimental pH values. Bacterial desorption was not affected by temperature (4-30°C) nor by an adsorbed layer of peptone and yeast extract on the substrata. The results indicate that bacterial desorption, hence bacterial removal during cleaning or their transfer via liquids flowing over colonized surfaces, is likely to vary with the surface composition and the bacterial species colonizing the surfaces.

  11. Organic contaminants in soil : desorption kinetics and microbial degradation

    Schlebaum, W.

    1999-01-01

    The availability of organic contaminants in soils or sediments for microbial degradation or removal by physical means (e.g.) soil washing or soil venting) depends on the desorption kinetics of these contaminants from the soil matrix. When the organic contaminants desorb very slow from the

  12. Influence of pre-treatments on the desorption isotherm ...

    Influence of pre-treatments on the desorption isotherm characteristics of plaintain. P-N T Johnson. Full Text: EMAIL FULL TEXT EMAIL FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT · http://dx.doi.org/10.4314/gjs.v39i1.15851 · AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for ...

  13. Electron Stimulated Desorption of Condensed Gases on Cryogenic Surfaces

    Tratnik, H; Hilleret, Noël

    2005-01-01

    In ultra-high vacuum systems outgassing from vacuum chamber walls and desorption from surface adsorbates are usually the factors which in°uence pressure and residual gas composition. In particular in beam vacuum systems of accelerators like the LHC, where surfaces are exposed to intense synchro- tron radiation and bombardment by energetic ions and electrons, properties like the molecular desorption yield or secondary electron yield can strongly in°uence the performance of the accelerator. In high-energy particle accelerators operating at liquid helium temperature, cold surfaces are exposed to the bombardment of energetic photons, electrons and ions. The gases released by the subsequent desorption are re-condensed on the cold surfaces and can be re-desorbed by the impinging electrons and ions. The equilibrium coverage reached on the surfaces exposed to the impact of energetic particles depends on the desorption yield of the condensed gases and can a®ect the operation of the accelerator by modifying th...

  14. Sorption and desorption of arsenate and arsenite on calcite

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  15. Sorption and desorption of indaziflam degradates in several agricultural soils

    Diego Gonçalves Alonso

    2016-04-01

    Full Text Available ABSTRACT Processes regulating pesticide fate in the environment are influenced by the physicochemical properties of pesticides and soils. Sorption and desorption are important processes as they regulate the movement of pesticides in soil. Although sorption-desorption is widely studied for herbicides, studies involving their metabolites in soil are scarce. Sorption and desorption of indaziflam metabolites (indaziflam-triazinediamine (FDAT, indaziflam-triazine-indanone (ITI and indaziflam-carboxilic acid (ICA were investigated in six Brazilian (BRA soils and three United States (USA soils with different physicochemical properties. The Freundlich equation described sorption of the metabolites for all soils (R2 > 0.98; 1/n ~ 1. Sorption order (Kf was ITI > ICA > FDAT. Mean values of Kf,oc were 453, 289, and 81 (BRA and 444, 48, and 48 (USA for metabolites ITI, ICA, and FDAT respectively. Desorption was hysteretic for all metabolites in all soils. These results suggest that these metabolites fall in the classification range of mobile to moderately mobile in soils.

  16. A monoenergetic electron source generated by nuclear stimulated desorption

    Kelson, I.; Levy, Y.; Nir, D.; Haustein, P.E.

    1994-01-01

    A series of measurements of nuclear stimulated desorption was performed for 103 Ru, using thin ruthenium films irradiated by thermal neutrons. The magnitude, time dependence and electric charge state of the outgoing 103m Rh flux was investigated. The utilization of monoenergetic electrons accompanying the 103 Rh decay for thin film thickness measurement is considered. (Author)

  17. Water absorption and desorption in shuttle ablator and insulation materials

    Whitaker, A. F.; Smith, C. F.; Wooden, V. A.; Cothren, B. E.; Gregory, H.

    1982-01-01

    Shuttle systems ablator and insulation materials underwent water soak with subsequent water desorption in vacuum. Water accumulation in these materials after a soak for 24 hours ranged from +1.1% for orbiter tile to +161% for solid rocket booster MSA-1. After 1 minute in vacuum, water retention ranged from none in the orbiter tile to +70% for solid rocket booster cork.

  18. Equilibrium adsorption data from temperature-programmed desorption measurements

    Foeth, F.; Mugge, J.M.; van der Vaart, R.; van der Vaart, Rick; Bosch, H.; Reith, T.

    1996-01-01

    This work describes a novel method that enables the calculation of a series of adsorption isotherms basically from a single Temperature-Programmed Desorption (TPD) experiment. The basic idea is to saturate an adsorbent packed in a fixed bed at a certain feed concentration and temperature and to

  19. PAH desorption from river floodplain soils using supercritical fluid extraction

    Yang, Y.; Cajthaml, Tomáš; Hofmann, T.

    2008-01-01

    Roč. 156, č. 3 (2008), s. 745-752 ISSN 0269-7491 R&D Projects: GA MŠk 2B06156 Institutional research plan: CEZ:AV0Z50200510 Keywords : pahs * slow desorption * carbonaceous materials Subject RIV: EE - Microbiology, Virology Impact factor: 3.135, year: 2008

  20. Study of boric acid sorption and desorption processes

    Czosnowska, B.; Laren, E.

    1978-01-01

    The results are given of the experimental determination of the effect on the boric acid flow and sorption and desorption efficiency of the flow rate of boric acid at different concentrations through an ion exchange column 10.2 cm 2 in cross section. The strongly alkaline VOFATIT RO ion exchanger was used. (B.S.)

  1. Experimental study on desorption characteristics of SAPO-34 and ZSM-5 zeolite

    Yuan, Z. X.; Zhang, X.; Wang, W. C.; Du, C. X.; Liu, Z. B.; Chen, Y. C.

    2018-03-01

    The dynamic characteristics of SAPO-34 and ZSM-5 zeolite in the desorption process have been experimentally studied with the gravimetric method. The weight change of the test sample was recorded continually for different conditions of temperature and pressure. The curve of the desorption degree with the temperature and the pressure was obtained and discussed. With the intrinsic different micro-structure, the two zeolites showed distinguished characteristics of the desorption. In contrast to an S-shaped desorption curve of the SAPO-34, the ZSM-5 showed an exponential desorption curve. In comparison, the desorption characteristics of the ZSM-5 were better than that of the SAPO-34 in the temperature range of 40 °C 90 °C. Nevertheless, the effect of the pressure on the desorption degree was stronger for the SAPO-34 than for the ZSM-5. Further analysis revealed that the desorption speed was affected more strongly by the temperature than by the pressure.

  2. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion

    Katsuaki Tanabe

    2016-01-01

    Full Text Available We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  3. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  4. The hydrogen; L'hydrogene

    NONE

    2004-07-01

    The hydrogen as an energy system represents nowadays a main challenge (in a scientific, economical and environmental point of view). The physical and chemical characteristics of hydrogen are at first given. Then, the challenges of an hydrogen economy are explained. The different possibilities of hydrogen production are described as well as the distribution systems and the different possibilities of hydrogen storage. Several fuel cells are at last presented: PEMFC, DMFC and SOFC. (O.M.)

  5. ITER Task T227 (1995): Solubility, diffusion, and desorption of hydrogen isotopes in beryllium and tungsten

    Thompson, D.A.; Macauley-Newcombe, R.G.

    1996-04-01

    This report contains results of thermal absorption and ion-beam analysis experiments performed in 1995 for ITER task T227. The materials studies were Be, BeO and W. The Be samples used are single crystals provided by Dr. H. Kawamura of J.A.E.R.I.; the BeO samples are polycrystalline semiconductor substrates provided by the Brush Wellman Company (USA); and the W samples are single crystals and are-melted polycrystals from the Johnson-Matthey Company (USA). All samples are very high purity and 100% density. (author) 16 refs., 1 tab., 10 figs

  6. Sorption and desorption of carbamazepine from water by smectite clays.

    Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

    2010-11-01

    Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Investigations into ultraviolet matrix-assisted laser desorption

    Heise, Theodore W. [Iowa State Univ., Ames, IA (United States)

    1993-07-01

    Matrix-assisted laser desorption (MALD) is a technique for converting large biomolecules into gas phase ions. Some characteristics of the commonly used uv matrices are determined. Solubilities in methanol range from 0.1 to 0.5 M. Solid phase absorption spectra are found to be similar to solution, but slightly red-shifted. Acoustic and quartz crystal microbalance signals are investigated as possible means of uv-MALD quantitation. Evidence for the existence of desorption thresholds is presented. Threshold values are determined to be in the range of 2 to 3 MW/cm2. A transient imaging technique based on laser-excited fluorescence for monitoring MALD plumes is described. Sensitivity is well within the levels required for studying matrix-assisted laser desorption, where analyte concentrations are significantly lower than those in conventional laser desorption. Results showing the effect of film morphology, particularly film thickness, on plume dynamics are presented. In particular, MALD plumes from thicker films tend to exhibit higher axial velocities. Fluorescent labeling of protein and of DNA is used to allow imaging of their uv-MALD generated plumes. Integrated concentrations are available with respect to time, making it possible to assess the rate of fragmentation. The spatial and temporal distributions are important for the design of secondary ionization schemes to enhance ion yields and for the optimization of ion collection in time-of-flight MS instruments to maximize resolution. Such information could also provide insight into whether ionization is closely associated with the desorption step or whether it is a result of subsequent collisions with the matrix gas (e.g., proton transfer). Although the present study involves plumes in a normal atmosphere, adaptation to measurements in vacuum (e.g., inside a mass spectrometer) should be straightforward.

  8. Nuclear stimulated desorption as a potential tool for surface study

    Nir, Dror.

    1993-03-01

    The described research work constitutes a base for an experimental method to be implemented in the study of solid surfaces. Nuclear Stimulated Desorption (NSD) is a new mode of experimentation in thin film and surface physics. It Is based on the interplay between nuclear phenomena (reactions and spontaneous decays), and atomic - scale induced effects on surfaces and very thin films. One may distinguish between two generically different relationships between the two. First, the dynamics of the nuclear reaction -primarily the recoil of the nucleus - may effect the position of the atom or molecule containing it. Second, the nuclear reaction (or decay) may serve as an analytical indicator of the whereabouts of the atom, or molecule, in question. In nuclear stimulated desorption, both thee aspects combine in an essential way. Namely, one employs a series of two consecutive decays (normally weak decays or isomeric transition) . The first of these decays causes the nucleus to desorb from a surface onto which it had been placed; the second serves to determine the position of the daughter and thereby the characteristics of the primary desorption . The essential feature in NSD is that it occurs almost exclusively from the outermost surface layer. This is because we choose to work with nuclei whose recoil energy Is of the same order of magnitude of the binding energy of the atom to the surface . Furthermore, the desorption probability and its angular (and temporal) characteristics, depend on the features (topology, morphology) of its immediate neighborhood. This work describes experiments which were designed to give relevant, phenomenological information about the outgoing flux of the radioactive daughters (for specifically chosen nuclear species) , and in particular the magnitude of the flux, its time dependence and its charged state. In addition. the basic phenomena itself is being distinguished from competing processes (thermal desorption, in particular). We will now

  9. Memory for Items and Relationships among Items Embedded in Realistic Scenes: Disproportionate Relational Memory Impairments in Amnesia

    Hannula, Deborah E.; Tranel, Daniel; Allen, John S.; Kirchhoff, Brenda A.; Nickel, Allison E.; Cohen, Neal J.

    2014-01-01

    Objective The objective of this study was to examine the dependence of item memory and relational memory on medial temporal lobe (MTL) structures. Patients with amnesia, who either had extensive MTL damage or damage that was relatively restricted to the hippocampus, were tested, as was a matched comparison group. Disproportionate relational memory impairments were predicted for both patient groups, and those with extensive MTL damage were also expected to have impaired item memory. Method Participants studied scenes, and were tested with interleaved two-alternative forced-choice probe trials. Probe trials were either presented immediately after the corresponding study trial (lag 1), five trials later (lag 5), or nine trials later (lag 9) and consisted of the studied scene along with a manipulated version of that scene in which one item was replaced with a different exemplar (item memory test) or was moved to a new location (relational memory test). Participants were to identify the exact match of the studied scene. Results As predicted, patients were disproportionately impaired on the test of relational memory. Item memory performance was marginally poorer among patients with extensive MTL damage, but both groups were impaired relative to matched comparison participants. Impaired performance was evident at all lags, including the shortest possible lag (lag 1). Conclusions The results are consistent with the proposed role of the hippocampus in relational memory binding and representation, even at short delays, and suggest that the hippocampus may also contribute to successful item memory when items are embedded in complex scenes. PMID:25068665

  10. The food, fuel, and financial crises affect the urban and rural poor disproportionately: a review of the evidence.

    Ruel, Marie T; Garrett, James L; Hawkes, Corinna; Cohen, Marc J

    2010-01-01

    The vulnerability of the urban poor to the recent food and fuel price crisis has been widely acknowledged. The unfolding global financial crisis, which brings higher unemployment and underemployment, is likely to further intensify this vulnerability. This paper reviews the evidence concerning the disproportionate vulnerability of the urban compared with the rural poor to these types of shocks. It reviews some of the unique characteristics of urban life that could make the urban poor particularly susceptible to price and financial shocks and summarizes the evidence regarding the disproportionate vulnerability of the urban poor. The focus is on impacts on poverty, food insecurity, and malnutrition. The review shows that although the urban poor are clearly one of the population groups most affected by the current (and previous) crises, the rural poor, landless, and net buyers are in no better position to confront the crisis without significant suffering. The poorest of the poor are the ones who will be most affected, irrespective of the continent, country, or urban or rural area where they live. The magnitude and severity of their suffering depends on their ability to adapt and on the specific nature, extent, and duration of the coping strategies they adopt. A better understanding of how these coping strategies are used and staggered is critical to help design triggers for action that can prevent households from moving to more desperate measures. Using these early coping strategies as early warning indicators could help prevent dramatic losses in welfare.

  11. Household expenditures on dietary supplements sold for weight loss, muscle building, and sexual function: Disproportionate burden by gender and income.

    Austin, S Bryn; Yu, Kimberly; Liu, Selena Hua; Dong, Fan; Tefft, Nathan

    2017-06-01

    Dietary supplements sold for weight loss (WL), muscle building (MB), and sexual function (SF) are not medically recommended. They have been shown to be ineffective in many cases and pose serious health risks to consumers due to adulteration with banned substances, prescription pharmaceuticals, and other dangerous chemicals. Yet no prior research has investigated how these products may disproportionately burden individuals and families by gender and socioeconomic position across households. We investigated household (HH) cost burden of dietary supplements sold for WL, MB, and SF in a cross-sectional study using data from 60,538 U.S. households (HH) in 2012 Nielsen/IRi National Consumer Panel, calculating annual HH expenditures on WL, MB, and SF supplements and expenditures as proportions of total annual HH income. We examined sociodemographic patterns in HH expenditures using Wald tests of mean differences across subgroups. Among HH with any expenditures on WL, MB, or SF supplements, annual HH first and ninth expenditure deciles were, respectively: WL $5.99, $145.36; MB $6.99, $141.93; and SF $4.98, $88.52. Conditional on any purchases of the products, female-male-headed HH spent more on WL supplements and male-headed HH spend more on MB and SF supplements compared to other HH types ( p -values supplements types ( p -values supplements ( p -values supplements sold for WL, MB, and SF disproportionately burden HH by income and gender.

  12. Changes in mechanical properties following cyclic prestressing of martensitic steel containing vanadium carbide in presence of nondiffusible hydrogen

    Kaneko, Mao; Doshida, Tomoki [Graduate School of Science and Technology, Sophia University, Tokyo 102-8554 (Japan); Takai, Kenichi, E-mail: takai@me.sophia.ac.jp [Department of Engineering and Applied Science, Sophia University, Tokyo 102-8554 (Japan)

    2016-09-30

    Changes in the states of nondiffusible hydrogen and mechanical properties after cyclic prestressing in the presence of only nondiffusible hydrogen were examined for martensitic steel containing vanadium carbide. The relationship between the change in the state of nondiffusible hydrogen and mechanical properties was also investigated. The hydrogen desorption profile in the high-temperature range decreased and that in the low-temperature range increased with increasing stress amplitude during cyclic prestressing in the presence of only nondiffusible hydrogen. Thus, the application of cyclic prestressing changed the state of hydrogen from a stable to an unstable one because of vacancies and their clusters. Hydrogen embrittlement susceptibility after cyclic prestressing increased with increasing stress amplitude and number of prestressing cycles in the presence of only nondiffusible hydrogen. This relationship indicates that hydrogen embrittlement susceptibility increased with the increasing amount of hydrogen detrapped from trap sites of nondiffusible hydrogen during cyclic prestressing. These results revealed that nondiffusible hydrogen easily detrapped from vanadium carbide due to the application of cyclic prestress and probably interacted with vacancies and their clusters, thus increasing hydrogen embrittlement susceptibility. The change of nondiffusible hydrogen to diffusible hydrogen and accumulation of vacancies and their clusters during cyclic prestressing are concluded to be the dominant factors in hydrogen embrittlement after the application of cyclic prestress.

  13. Hydrogen-induced amorphization of SmFe{sub 3}

    Kubis, M.; Handstein, A.; Gebel, B.; Gutfleisch, O.; Mueller, K.-H.; Schultz, L. [Institut fuer Festkoerper- und Werkstofforschung Dresden e.V. (Germany). Inst. fuer Metallische Werkstoffe

    2000-07-01

    The hydrogen absorption behavior of SmFe{sub 3} (PuNi{sub 3}-type structure) was observed in the range from 0.05 to 4 MPa by differential scanning calorimetry. The structural changes were observed by X-ray diffraction measurements. For pressures below 0.8 MPa two exothermic reactions were found which are attributed (i) to the interstitial absorption and (ii) to the disproportionation into SmH{sub 2} and {alpha}-Fe. For higher hydrogen pressures, the second exothermic peak occured at significantly lower temperatures and splitted into two peaks. The first one was identified as the exothermic signal of the hydrogen-induced amorphization of the SmFe{sub 3} hydride. The second peak is caused by the precipitation of SmH{sub 2} and {alpha}-Fe from the amorphous material. (orig.)

  14. Optical hydrogen sensors based on metal-hydrides

    Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

    2012-06-01

    For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

  15. Hydrogen energy in changing environmental scenario: Indian context

    Leo Hudson, M. Sterlin; Dubey, P.K.; Pukazhselvan, D.; Pandey, Sunil Kumar; Singh, Rajesh Kumar; Raghubanshi, Himanshu; Shahi, Rohit R.; Srivastava, O.N.

    2009-01-01

    This paper deals with how the Hydrogen Energy may play a crucial role in taking care of the environmental scenario/climate change. The R and D efforts, at the Hydrogen Energy Center, Banaras Hindu University have been described and discussed to elucidate that hydrogen is the best option for taking care of the environmental/climate changes. All three important ingredients for hydrogen economy, i.e., production, storage and application of hydrogen have been dealt with. As regards hydrogen production, solar routes consisting of photoelectrochemical electrolysis of water have been described and discussed. Nanostructured TiO 2 films used as photoanodes have been synthesized through hydrolysis of Ti[OCH(CH 3 ) 2 ] 4 . Modular designs of TiO 2 photoelectrode-based PEC cells have been fabricated to get high hydrogen production rate (∝10.35 lh -1 m -2 ). However, hydrogen storage is a key issue in the success and realization of hydrogen technology and economy. Metal hydrides are the promising candidates due to their safety advantage with high volume efficient storage capacity for on-board applications. As regards storage, we have discussed the storage of hydrogen in intermetallics as well as lightweight complex hydride systems. For intermetallic systems, we have dealt with material tailoring of LaNi 5 through Fe substitution. The La(Ni l-x Fe x ) 5 (x = 0.16) has been found to yield a high storage capacity of ∝2.40 wt%. We have also discussed how CNT admixing helps to improve the hydrogen desorption rate of NaAlH 4 . CNT (8 mol%) admixed NaAlH 4 is found to be optimum for faster desorption (∝3.3 wt% H 2 within 2 h). From an applications point of view, we have focused on the use of hydrogen (stored in intermetallic La-Ni-Fe system) as fuel for Internal Combustion (IC) engine-based vehicular transport, particularly two and three-wheelers. It is shown that hydrogen used as a fuel is the most effective alternative fuel for circumventing climate change. (author)

  16. Adsorption-desorption and leaching of pyraclostrobin in Indian soils.

    Reddy, S Navakishore; Gupta, Suman; Gajbhiye, Vijay T

    2013-01-01

    Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL(-1). The distribution coefficient (Kd) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (Kd 18.26), followed by Vertisol (Kd 9.87) and Inceptisol (Kd 4.91). KF value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. Kd values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL(-1). Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1-25.3%, 9.4-20.7% and 8.1-13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow

  17. Influence of cold deformation and annealing on hydrogen embrittlement of cold hardening bainitic steel for high strength bolts

    Hui, Weijun, E-mail: wjhui@bjtu.edu.cn [School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing 100044 (China); Zhang, Yongjian; Zhao, Xiaoli; Shao, Chengwei [School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing 100044 (China); Wang, Kaizhong; Sun, Wei; Yu, Tongren [Technical Center, Maanshan Iron & Steel Co., Ltd., Maanshan 243002, Anhui (China)

    2016-04-26

    The influence of cold drawing and annealing on hydrogen embrittlement (HE) of newly developed cold hardening bainitic steel was investigated by using slow strain rate testing (SSRT) and thermal desorption spectrometry (TDS), for ensuring safety performance of 10.9 class high strength bolts made of this kind of steel against HE under service environments. Hydrogen was introduced into the specimen by electrochemical charging. TDS analysis shows that the hydrogen-charged cold drawn specimen exhibits an additional low-temperature hydrogen desorption peak besides the original high-temperature desorption peak of the as-rolled specimen, causing remarkable increase of absorbed hydrogen content. It is found that cold drawing significantly enhances the susceptibility to HE, which is mainly attributed to remarkable increase of diffusible hydrogen absorption, the occurrence of strain-induced martensite as well as the increase of strength level. Annealing after cold deformation is an effective way to improve HE resistance and this improvement strongly depends on annealing temperature, i.e. HE susceptibility decreases slightly with increasing annealing temperature up to 200 °C and then decreases significantly with further increasing annealing temperature. This phenomenon is explained by the release of hydrogen, the recovery of cold worked microstructure and the decrease of strength with increasing annealing temperature.

  18. The study of hydrogen electrosorption in layered nickel foam/palladium/carbon nanofibers composite electrodes

    Skowronski, J.M.; Czerwinski, A.; Rozmanowski, T.; Rogulski, Z.; Krawczyk, P.

    2007-01-01

    In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support

  19. Ultrapure hydrogen thermal compressor based on metal hydrides for fuel cells and hybrid vehicles

    Almasan, V.; Biris, A.; Coldea, I.; Lupu, D.; Misan, I.; Popeneciu, G.; Ardelean, O.

    2007-01-01

    Full text: In hydrogen economy, efficient compressors are indispensable elements in the storage, transport and distribution of the produced hydrogen. Energetic efficient technologies can contribute to H 2 pipelines transport to the point of use and to distribute H 2 by refuelling stations. Characteristic for metal hydrides systems is the wide area of possibilities to absorb hydrogen at low pressure from any source of hydrogen, to store and deliver it hydrogen at high pressure (compression ratio more than 30). On the basis of innovative concepts and advanced materials for H 2 storage/compression (and fast thermal transfer), a fast mass (H 2 ) and heat transfer unit will be developed suitable to be integrated in a 3 stage thermal compressor. Metal hydrides used for a three stage hydrogen compression system must have different equilibrium pressures, namely: for stage 1, low pressure H 2 absorption and resistant to poisoning with impurities of hydrogen, for stage 2, medium pressure H 2 absorption and for stage 3, high pressure hydrogen delivery (120 bar). In the case of compression device based on metallic hydrides the most important properties are the hydrogen absorption/desorption rate, a smaller process enthalpy and a great structural stability on long term hydrogen absorption/desorption cycling. These properties require metal hydrides with large differences between the hydrogen absorption and desorption pressures at equilibrium, within a rather small temperature range. The main goal of this work is to search and develop metal hydride integrated systems for hydrogen purification, storage and compression. After a careful screening three hydrogen absorbing alloys will be selected. After selection, the work up of the alloys composition on the bases of detailed solid state studies, new multi-component alloys will be developed, with suitable thermodynamic and kinetic properties for a hydrogen compressor. The results of the study are the following: new types of hydrogen

  20. Photon- and electron-stimulated desorption from laboratory models of interstellar ice grains

    Thrower, J. D.; Abdulgalil, A. G. M.; Collings, M. P.; McCoustra, M. R. S.; Burke, D. J.; Brown, W. A.; Dawes, A.; Holtom, P. J.; Kendall, P.; Mason, N. J.; Jamme, F.; Fraser, H. J.; Rutten, F. J. M.

    2010-01-01

    The nonthermal desorption of water from ice films induced by photon and low energy electron irradiation has been studied under conditions mimicking those found in dense interstellar clouds. Water desorption following photon irradiation at 250 nm relies on the presence of an absorbing species within the H 2 O ice, in this case benzene. Desorption cross sections are obtained and used to derive first order rate coefficients for the desorption processes. Kinetic modeling has been used to compare the efficiencies of these desorption mechanisms with others known to be in operation in dense clouds.

  1. Properties of Mg-Al alloys in relation to hydrogen storage

    Andreasen, A.

    2005-01-01

    storage e.g. in stationary applications. In this report the properties of Mg-Al alloys are reviewed in relation to solid state hydrogen storage. Alloying with Al reduces the hydrogen capacity since Al doesnot form a hydride under conventional hydriding conditions, however both the thermodynamical......Magnesium theoretically stores 7.6 wt. % hydrogen, although it requires heating to above 300 degrees C in order to release hydrogen. This limits its use for mobile application. However, due to its low price and abundance magnesium should still beconsidered as a potential candidate for hydrogen...... properties (lower desorption temperature), and kinetics of hydrogenation/dehydrogenation are improved. In addition to this, the low price of the hydride isretained along with improved heat transfer properties and improved resistance towards oxygen contamination....

  2. Investigation of microstructure changes in ODS-EUROFER after hydrogen loading

    Emelyanova, O.V.; Ganchenkova, M.G.; Malitskii, E.; Yagodzinskyy, Y.N.; Klimenkov, M.; Borodin, V.A.; Vladimirov, P.V.; Lindau, R.; Möslang, A.; Hänninen, H.

    2016-01-01

    The effect of hydrogen on the microstructure of mechanically tested ODS-EUROFER steel was investigated by means of transmission electron microscopy, thermal desorption spectroscopy, and atomistic simulations. The presence of yttrium oxide particles notably increases hydrogen uptake in ODS-EUROFER steel as compared to ODS-free EUROFER 97. Under tensile loading, hydrogen accumulation promotes the loss of cohesion at the oxide particle interfaces. First-principles molecular dynamics simulations indicate that hydrogen can be trapped at nanoparticle/matrix interface, creating OH-groups. The accumulation of hydrogen atoms at the oxide particle surface can be the reason for the observed hydrogen-induced oxide/matrix interface weakening and de-cohesion under the action of external tensile stress.

  3. Properties of MgAl alloys in relation to hydrogen storage

    Andreasen, Anders

    2005-08-01

    Magnesium theoretically stores 7.6 wt. % hydrogen, although it requires heating to above 300 degrees C in order to release hydrogen. This limits its use for mobile application. However, due to its low price and abundance magnesium should still be considered as a potential candidate for hydrogen storage e.g. in stationary applications. In this report the properties of Mg-Al alloys are reviewed in relation to solid state hydrogen storage Alloying with Al reduces the hydrogen capacity since Al does not form a hydride under conventional hydriding conditions, however both the thermodynamical properties (lower desorption temperature), and kinetics of hydrogenation/dehydrogenation are improved. In addition to this, the low price of the hydride is retained along with improved heat transfer properties and improved resistance towards oxygen contamination. (au)

  4. Destructive hydrogenation

    Terrisse, H; Dufour, L

    1929-01-21

    Oils of high boiling point, e.g. gas oil, lamp oil, schist oil, brown coal tar etc., are converted into motor benzine by heating them at 200 to 500/sup 0/C under pressure of 5 to 40 kilograms/cm/sup 2/ in the presence of ferrous chloride and gases such as hydrogen, or water gas, the desulfurization of the oils proceeding simultaneously. One kilogram of lamp oil and 100 g. ferrous chloride are heated in an autoclave in the presence of water gas under a pressure of 18 kg/cm/sup 2/ to 380 to 400/sup 0/C. The gaseous products are allowed to escape intermittently and are replaced by fresh water gas. A product distilling between 35 and 270/sup 0/C is obtained.

  5. Microstructural evolution during hydrogen sorption cycling of Mg-FeTi nanolayered composites

    Kalisvaart, W.P., E-mail: pkalisvaart@gmail.com [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada); Kubis, Alan; Danaie, Mohsen; Amirkhiz, Babak Shalchi [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada); Mitlin, David, E-mail: dmitlin@ualberta.ca [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada)

    2011-03-15

    This paper describes the microstructural evolution of Mg-FeTi mutlilayered hydrogen storage materials during extended cycling. A 28 nm Mg-5 nm FeTi multilayer has comparable performance to a cosputtered material with an equivalent composition (Mg-10%Fe-10%Ti), which is included as a baseline case. At 200 deg. C, the FeTi layers act as a barrier, preventing agglomeration of Mg particles. At 300 deg. C, the initial structure of the multilayer is preserved up to 35 cycles, followed by fracturing of the Mg layers in the in-plane direction and progressive delamination of the FeTi layers as observed by electron microscopy. Concurrently, an increase in the Mg grain size was observed from 32 to 76 nm between cycles 35 and 300. As a result, the absorption kinetics deteriorate with cycling, although 90% of the total capacity is still absorbed within 2 min after as many as 300 cycles. The desorption kinetics, on the other hand, remain rapid and stable, and complete desorption of 4.6 wt.% H is achieved in 1.5 min at ambient desorption pressure. In addition to showing good hydrogen storage performance, multilayers are an excellent model system for studying the relation between microstructure and hydrogen absorption/desorption kinetics.

  6. Microstructural evolution during hydrogen sorption cycling of Mg-FeTi nanolayered composites

    Kalisvaart, W.P.; Kubis, Alan; Danaie, Mohsen; Amirkhiz, Babak Shalchi; Mitlin, David

    2011-01-01

    This paper describes the microstructural evolution of Mg-FeTi mutlilayered hydrogen storage materials during extended cycling. A 28 nm Mg-5 nm FeTi multilayer has comparable performance to a cosputtered material with an equivalent composition (Mg-10%Fe-10%Ti), which is included as a baseline case. At 200 deg. C, the FeTi layers act as a barrier, preventing agglomeration of Mg particles. At 300 deg. C, the initial structure of the multilayer is preserved up to 35 cycles, followed by fracturing of the Mg layers in the in-plane direction and progressive delamination of the FeTi layers as observed by electron microscopy. Concurrently, an increase in the Mg grain size was observed from 32 to 76 nm between cycles 35 and 300. As a result, the absorption kinetics deteriorate with cycling, although 90% of the total capacity is still absorbed within 2 min after as many as 300 cycles. The desorption kinetics, on the other hand, remain rapid and stable, and complete desorption of 4.6 wt.% H is achieved in 1.5 min at ambient desorption pressure. In addition to showing good hydrogen storage performance, multilayers are an excellent model system for studying the relation between microstructure and hydrogen absorption/desorption kinetics.

  7. Li-Al-borohydride as a potential candidate for on-board hydrogen storage

    Lindemann, Inge; Domenech Ferrer, Roger; Dunsch, Lothar; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, PO Box 270016, D-01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [University of Geneva, Crystallography and Physical Chemistry Department, 1211 Geneva (Switzerland)

    2010-07-01

    Recently, double-cation borohydride systems have attracted great interest. It was found that the desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by combination of appropriate cations. Li-Al-borohydride shows a desorption temperature suitable for applications ({approx} 70 C) combined with an high hydrogen density (17.2 wt.%). It was synthesised via high energy ball milling of AlCl{sub 3} and LiBH{sub 4}. The structure of the compound was obtained from high-resolution synchrotron powder diffraction and shows a unique complex structure within the borohydrides. The material was characterized by means of in-situ-Raman, DSC, TG and thermal desorption measurements to study its decomposition pathway. The desorption at {approx} 70 C results in the formation of LiBH{sub 4} while the high mass loss of about 20% points to the release of not only hydrogen but also diborane. This is right now the main drawback for applications because it hinders reversibility.

  8. Auger decay mechanism in photon-stimulated desorption of ions from surfaces

    Parks, C.C.

    1983-11-01

    Photon-stimulated desorption (PSD) of positive ions was studied with synchrotron radiation using an angle-integrating time-of-flight mass spectrometer. Ion yields as functions of photon energy near core levels were measured from condensed gases, alkali fluorides, and other alkali and alkaline earth halides. These results are compared to bulk photoabsorption measurements with emphasis on understanding fundamental desorption mechanisms. The applicability of the Auger decay mechanism, in which ion desorption is strictly proportional to surface absorption, is discussed in detail. The Auger decay model is developed in detail to describe Na + and F + desorption from NaF following Na(1s) excitation. The major decay pathways of the Na(1s) hole leading to desorption are described and equations for the energetics of ion desorption are developed. Ion desorption spectra of H + , Li + , and F + are compared to bulk photoabsorption near the F(2s) and Li(1s) edges of LiF. A strong photon beam exposure dependence of ion yields from alkali fluorides is revealed, which may indicate the predominance of metal ion desorption from defect sites. The large role of indirect mechanisms in ion desorption condensed N 2 -O 2 multilayers is demonstrated and discussed. Ion desorption spectra from several alkali halides and alkaline earth halides are compared to bulk photoabsorption spectra. Relative ion yields from BaF 2 and a series of alkali halides are discussed in terms of desorption mechanisms

  9. Adsorption and desorption of phosphorus in ceramic capsules

    Almeida, J.R.F. de.

    1983-01-01

    Experiments were carried out in order to analyse the capacity of adsorving P from water using ceramic capsules with 32P, in the presence and absence of water flow through the capsule. Also studied was the desorption of 32 P from the capsule in water, with and without water flow. The desorption of residual 32 P was analysed by isotopic exchange with 31 P, also with and without water flow. It was observed that, in the presence of a flow, the capsule retained 32 P from the solution, which was weakly desorbed by water but was isotopically exchanged with 31 P. In the absence of a flow, the capsule was not an efficient P adsorber. (Author) [pt

  10. Energetic particle induced desorption of water vapor cryo-condensate

    Menon, M.M.; Owen, L.W.; Simpkins, J.E.; Uckan, T.; Mioduszewski, P.K.

    1990-01-01

    An in-vessel cryo-condensation pump is being designed for the Advanced Divertor configuration of the DIII-D tokamak. To assess the importance of possible desorption of water vapor from the cryogenic surfaces of the pump due to impingement of energetic particles from the plasma, a 77 K surface on which a thin layer of water vapor was condensed was exposed to a tenuous plasma (density = 2 x 10 10 cm -3 , electron temperature = 3 eV). Significant desorption of the condensate occurred, suggesting that impingement of energeticparticles (10 eV) at flux levels of ∼10 16 cm 2 s -1 on cryogenic surfaces could potentially induce impurity problems in the tokamak plasma. A pumping configuration is presented in which this problem is minimized without sacrificing the pumping speed

  11. Investigations on ion-beam induced desorption from cryogenic surfaces

    Maurer, Christoph

    2017-01-01

    A central component of FAIR, the Facility for Antiproton and Ion Research, will be the superconducting heavy ion synchrotron SIS100, which is supposed to provide reliable, high intensity beams for various applications. Its beam intensity is governed by the space charge limit, while the maximum energy is determined by the machine's magnetic rigidity. That means, ions with higher charge state can be accelerated to a higher energy, but with less intensity. For highest intensity beams, intermediate charge states have to be used instead of high charge state ions. This alleviates the issue of space charge but gives rise to dynamic vacuum effects, which also limit beam intensity: beam particles collide with residual gas particles, which leads to charge exchange and their subsequent loss. Impacting on the chamber wall, these ions release adsorbed gas particles. This process is called desorption and leads to a localized increase in pressure, which in turn causes more charge exchange. After a few rounds of self amplification, this can lead to total beam loss. This ''runaway-desorption'' is typically the main beam intensity limiting process for intermediate charge state (heavy) ion beams. The extent of this phenomenon is governed by two factors: the initial beam intensity and the desorption yield. The latter is examined within the scope of this thesis. Special emphasis is placed on the influence of the target's temperature, since the SIS100 will be a superconducting machine with cryogenic vacuum chamber walls. In order to investigate this topic, an experimental setup has been devised, built at the SIS18 and taken into commission. Based on the experience gained during operation, it has been continuously improved and extended. Another central innovation presented in this thesis is the use of gas dynamics simulations for an improved method of data analysis. Using this technique, environmental conditions like the chamber geometry and the connected

  12. Spatially resolved thermal desorption/ionization coupled with mass spectrometry

    Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S

    2013-02-26

    A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.

  13. Electron stimulated desorption study of oxygen adsorption on tungsten

    Prince, R.H.; Floyd, G.R.

    1978-01-01

    The adsorption of oxygen on a polycrystalline tungsten surface at approximately 800 K has been studied by means of electron stimulated desorption (ESD). Although precision gas dosing was not employed, the initial sticking probability for dissociative adsorption appears to be essentially unity, while the variation with coverage suggests that a high degree of order exists and that precursor state kinetics are significant. A most noticeable and reproducible discontinuity in ESD parameters occurs at a fractional coverage theta approximately 0.8 (exposure approximately 1.4 X 10 15 molecules/cm 2 incident) which is interpreted as an order-disorder transition within a single (β 1 ) chemisorption state, and results in an increase in the ionic desorption cross-section by a factor of approximately 1.26. A discussion of the adsorption kinetics and the disorder transition is given in terms of current models of dissociative adsoption which include the effects of nearest neighbour lateral interactions. (Auth.)

  14. Unconventional resource's production under desorption-induced effects

    S. Sina Hosseini Boosari

    2016-06-01

    We have developed a numerical model to study the effect of changes in porosity, permeability and compaction on four major U.S. shale formations considering their Langmuir isotherm desorption behavior. These resources include; Marcellus, New Albany, Barnett and Haynesville Shales. First, we introduced a model that is a physical transport of single-phase gas flow in shale porous rock. Later, the governing equations are implemented into a one-dimensional numerical model and solved using a fully implicit solution method. It is found that the natural gas production is substantially affected by desorption-induced porosity/permeability changes and geomechancis. This paper provides valuable insights into accurate modeling of unconventional reservoirs that is more significant when an even small correction to the future production prediction can enormously contribute to the U.S. economy.

  15. Desorption and ionization processes in laser mass spectrometry

    Peyl, G.J.Q. van der.

    1984-01-01

    In this thesis results are reported from a study on the desorption- and ionization process initiated by infra-red laser irradiation (LDMS) or ion bombardment (SIMS) of thin organic sample layers. The study is especially focused on the formation of quasimolecular ions under these conditions. Results of these investigations can be used for a better optimization of the LDMS and SIMS techniques in organic mass spectrometry. First, an overview is given of laser desorption mass spectrometry. Next, the coupling of the laser energy into the organic sample layer is investigated. It is concluded that the laser energy is primarily absorbed by the substrate material and not by the organic overlayer. The formation of quasi-molecular ions, either in the gas phase or in the substrate surface is investigated. The final section reports kinetic energy distributions for ions sputtered from organic solids and liquids. (Auth.)

  16. Sorption/desorption reversibility of polycyclic aromatic hydrocarbons (PAHs) in soils and carbonaceous materials

    Wang, Guohui

    2008-07-01

    Understanding sorption/desorption is an important prerequisite for the prediction of fate and transport of pollutants in the environment. During the last two decades, numerous studies have reported hysteresis phenomenon for the interaction of hydrophobic organic contaminants (HOCs) with natural organic matter (NOM). It manifests as nonsingular sorption/desorption isotherms or different rates for sorption and desorption, where during desorption a higher affinity of a compound on a given sorbent and a longer time scale for release than for sorption is observed. Other studies showed that some of the reported sorption/desorption hysteresis phenomena are due to experimental artifacts, mainly resulting from non-attainment of sorption equilibrium before desorption experiments, which result in 'pseudo-hysteresis'. Except for the hypothesis of sorbent reconfiguration, clear experimental evidence for the physical or chemical mechanisms proposed to lead to hysteresis is still lacking. In this study, sorption/desorption equilibrium and kinetics of phenanthrene sorption/desorption from two soils and three carbonaceous samples were investigated using both batch and column techniques. The main objective of this work was to monitor hysteresis phenomenon by carefully recovering the solute mass in the system and to compare sorption/desorption equilibria and kinetics thermodynamically. Nonsingular isotherms and higher desorption enthalpies as well as increased activation energies with proceeding desorption are expected if significant hysteresis exists. Sorption-desorption cycles were carried out to compare equilibrium isotherms and associated sorption/desorption enthalpies (AeH, isosteric heats). Instead of the traditional decant-and-refill batch method, the experiments were conducted using a newly designed batch protocol, which enables the determination of sorption/desorption isotherms at different temperatures using a closed batch system. This method additionally allows

  17. Sorption/desorption reversibility of polycyclic aromatic hydrocarbons (PAHs) in soils and carbonaceous materials

    Wang, Guohui

    2008-07-01

    Understanding sorption/desorption is an important prerequisite for the prediction of fate and transport of pollutants in the environment. During the last two decades, numerous studies have reported hysteresis phenomenon for the interaction of hydrophobic organic contaminants (HOCs) with natural organic matter (NOM). It manifests as nonsingular sorption/desorption isotherms or different rates for sorption and desorption, where during desorption a higher affinity of a compound on a given sorbent and a longer time scale for release than for sorption is observed. Other studies showed that some of the reported sorption/desorption hysteresis phenomena are due to experimental artifacts, mainly resulting from non-attainment of sorption equilibrium before desorption experiments, which result in 'pseudo-hysteresis'. Except for the hypothesis of sorbent reconfiguration, clear experimental evidence for the physical or chemical mechanisms proposed to lead to hysteresis is still lacking. In this study, sorption/desorption equilibrium and kinetics of phenanthrene sorption/desorption from two soils and three carbonaceous samples were investigated using both batch and column techniques. The main objective of this work was to monitor hysteresis phenomenon by carefully recovering the solute mass in the system and to compare sorption/desorption equilibria and kinetics thermodynamically. Nonsingular isotherms and higher desorption enthalpies as well as increased activation energies with proceeding desorption are expected if significant hysteresis exists. Sorption-desorption cycles were carried out to compare equilibrium isotherms and associated sorption/desorption enthalpies (AeH, isosteric heats). Instead of the traditional decant-and-refill batch method, the experiments were conducted using a newly designed batch protocol, which enables the determination of sorption/desorption isotherms at different temperatures using a closed batch system. This method additionally allows the

  18. Hydrogen Storage using Metal Hydrides in a Stationary Cogeneration System

    Botzung, Maxime; Chaudourne, Serge; Perret, Christian; Latroche, Michel; Percheron-Guegan, Annick; Marty Philippe

    2006-01-01

    In the frame of the development of a hydrogen production and storage unit to supply a 40 kW stationary fuel cell, a metal hydride storage tank was chosen according to its reliability and high energetic efficiency. The study of AB5 compounds led to the development of a composition adapted to the project needs. The absorption/desorption pressures of the hydride at 75 C (2 / 1.85 bar) are the most adapted to the specifications. The reversible storage capacity (0.95 %wt) has been optimized to our work conditions and chemical kinetics is fast. The design of the Combined Heat and Power CHP system requires 5 kg hydrogen storage but in a first phase, only a 0.1 kg prototype has been realised and tested. Rectangular design has been chosen to obtain good compactness with an integrated plate fin type heat exchanger designed to reach high absorption/desorption rates. In this paper, heat and mass transfer characteristics of the Metal Hydride tank (MH tank) during absorption/desorption cycles are given. (authors)

  19. Design and integration of a hydrogen storage on metallic hydrides

    Botzung, M.

    2008-01-01

    This work presents a hydrogen storage system using metal hydrides for a Combined Heat and Power (CHP) system. Hydride storage technology has been chosen due to project specifications: high volumetric capacity, low pressures (≤ 3.5 bar) and low temperatures (≤ 75 C: fuel cell temperature). During absorption, heat from hydride generation is dissipated by fluid circulation. An integrated plate-fin type heat exchanger has been designed to obtain good compactness and to reach high absorption/desorption rates. At first, the storage system has been tested in accordance with project specifications (absorption 3.5 bar, desorption 1.5 bar). Then, the hydrogen charge/discharge times have been decreased to reach system limits. System design has been used to simulate thermal and mass comportment of the storage tank. The model is based on the software Fluent. We take in consideration heat and mass transfers in the porous media during absorption/desorption. The hydride thermal and mass behaviour has been integrated in the software. The heat and mass transfers experimentally obtained have been compared to results calculated by the model. The influence of experimental and numerical parameters on the model behaviour has also been explored. (author) [fr

  20. Cellular automaton model for hydrogen transport dynamics through metallic surface

    Shimura, K.; Yamaguchi, K.; Terai, T.; Yamawaki, M.

    2002-01-01

    Hydrogen re-emission and re-combination at the surface of first wall materials are a crucial issue for the understanding of the fuel recycling and for the tritium inventory in plasma facing materials. It is know to be difficult to model the transient behaviour of those processes due to their complex time-transient nature. However, cellular automata (CA) are powerful tools to model such complex systems because of their nature of discreteness in both dependent and independent variables. Then the system can be represented by the fully local interactions between cells. For that reason, complex physical and chemical systems can be described by fairly simple manner. In this study, the kinetics of desorption of adsorbed hydrogen from an ideal metallic surface is modelled in CA. Thermal desorption is simulated with this model and the comparison with the theory of rate processes is performed to identify the validity of this model. The overall results show that this model is reasonable to express the desorption kinetics

  1. Influence of the evaporation rate and the evaporation mode on the hydrogen sorption kinetics of air-exposed magnesium films

    Leon, A.; Knystautas, E.J.; Huot, J.; Schulz, R.

    2006-01-01

    It has been shown that the hydrogen sorption properties of air-exposed magnesium films are influenced by the deposition parameters such as the evaporation rate or the evaporation mode used during their preparation. As the evaporation rate increases, the structure of the film tends to be highly oriented along the [002] direction and the kinetics of hydrogen absorption and desorption are faster. Moreover, the hydrogen sorption kinetics of magnesium films prepared with an electron beam source under a high vacuum are faster by almost a factor of two compared to those prepared using resistive heating under low vacuum. These two parameters reduce drastically the activation and the incubation period during hydrogen absorption and desorption, respectively

  2. Sample and plume luminescence in fast heavy ion induced desorption

    Tuszynski, W.; Koch, K.; Hilf, E.R.

    1996-01-01

    The luminescence arising in 252 Cf-fission fragment induced desorption events has been measured using the time-correlated single photon counting technique. Photons emitted from the sample have been guided from a plasma desorption ion source to a photodetector by an optical fibre. Spectra and decay functions have been obtained using thin layers of Coronene or POPOP as samples. The results are strongly dependent on the acceleration field applied for ion extraction. Approximately 10 photons per fission fragment have been produced when applying no accelerating voltage. The results clearly show that these photons come from radiative electronic relaxations of molecules in the solid sample. Considerably more photons per fission fragment have been produced when applying a positive acceleration voltage. The intensity increases almost linearly for acceleration fields below 10 kV/cm and saturates at a nearly 10-fold higher value when compared to no acceleration. The intensity is also affected by the homogeneity of the accelerating field. These additional photons are attributed to radiative electronic relaxations of desorbed neutral molecules in the plume excited by inelastic collisions with accelerated positive ions. No additional photons have been observed when extracting negative ions. The negative ions produced do obviously not hit and/or excite desorbed neutral molecules, presumably due to their specific desorption characteristics. The experimental data have been analyzed by comparing with the cw and time-resolved sample luminescence obtained by optical excitation. The findings demonstrate that valuable information on ion-solid interactions, on specific desorption quantities and on processes in the plume can be obtained by measuring and analyzing the luminescence induced by the impact of high energy primary ions. (orig.)

  3. Hydrogen storage in hybrid of layered double hydroxides/reduced graphene oxide using spillover mechanism

    Ensafi, Ali A.; Jafari-Asl, Mehdi; Nabiyan, Afshin; Rezaei, Behzad; Dinari, Mohammad

    2016-01-01

    New efficient hydrogen storage hybrids were fabricated based on hydrogen spillover mechanism, including chemisorptions and dissociation of H_2 on the surface of LDH (layered double hydroxides) and diffusion of H to rGO (reduced graphene oxide). The structures and compositions of all of the hybrids (LDHs/rGO) have been verified using different methods including transmission electron microscopy, X ray diffraction spectroscopy, infrared spectroscopy and Brunauer–Emmett–Teller analysis. Then, the abilities of the LDHs/rGOs, as hydrogen spillover, were investigated by electrochemical methods. In addition, the LDHs/rGOs were decorated with palladium, using redox replacement process, and their hydrogen spillover properties were studied. The results showed that the hydrogen adsorption/desorption kinetics, hydrogen storage capacities and stabilities of Pd"#LDH/rGOs are better than Pd/rGO. Finally presence of different polymers (synthesis with monomers, 4–aminophenol, 4–aminothiophenol, o-phenylenediamine and p-phenylenediamine) at the surface of the Pd#LDH/rGOs on hydrogen storage were studied. The results showed that presence of o-phenylenediamine and p-phenylenediamine improves the kinetics of the hydrogen adsorption/desorption and increase the capacity of the hydrogen storage. - Highlights: • Efficient hydrogen storage sorbents are introduced. • The sorbents are synthesized based on hybrids of layered double hydroxide. • The compositions of all of the hybrids are verified using different methods. • Pd nanoparticles modified nanohybrids are investigated for hydrogen storage. • Presence of different polymers beside the hydrogen sorbents are investigated.

  4. Study of the mechanisms of heavy-ion induced desorption on accelerator-relevant materials; Untersuchung der Mechanismen schwerioneninduzierter Desorption an beschleunigerrelevanten Materialien

    Bender, Markus

    2008-02-22

    The ion beam loss induced desorption is a performance limitation for low charge state heavy ion accelerators. If charge exchanged projectile ions get lost onto the beam pipe, desorption of gas is stimulated resulting in a pressure increase inside of the synchrotron and thus, a dramatically reduction of the beam life time. To minimize the amount of desorbed gas an experimental program has been started to measure the desorption yields (released gas molecules per incident ion) of various materials and different projectile ions. The present work is a contribution to the understanding of the physical processes behind the ion beam loss induced desorption. The yield measurements by the pressure rise method have been combined for the rst time with in situ ion beam analysis technologies such as ERDA and RBS. With this unique method the desorption behavior of a sample can be correlated to its surface and bulk properties. The performed experiments with 1,4 MeV/u Xenon-Ions show that the ion induced desorption is mainly a surface effect. Sputtered oxide layers or impurities do not contribute to the desorbed gas significantly. Nevertheless bulk properties play an important role in the desorption strength. Pure metallic samples desorb less gas than isolating materials under swift heavy ion irradiation. From the experimental results it was possible to estimate the desorption yields of various materials under ion bombardment by means of an extended inelastic thermal-spike-model. The extension is the combination of the thermal-spike's temperature map with thermal desorption. Within this model the ion induced desorption can be regarded as the release of adsorbates from a transient overheated spot on the samples surface around the ion impact. Finally a copper substrate with a gold coated surface was developed and proposed as a suitable material for a beam loss collimator with minimum desorption to ensure the performance of GSI's SIS18 in high current beam operation. (orig.)

  5. The desorptivity model of bulk soil-water evaporation

    Clapp, R. B.

    1983-01-01

    Available models of bulk evaporation from a bare-surfaced soil are difficult to apply to field conditions where evaporation is complicated by two main factors: rate-limiting climatic conditions and redistribution of soil moisture following infiltration. Both factors are included in the "desorptivity model', wherein the evaporation rate during the second stage (the soil-limiting stage) of evaporation is related to the desorptivity parameter, A. Analytical approximations for A are presented. The approximations are independent of the surface soil moisture. However, calculations using the approximations indicate that both soil texture and soil moisture content at depth significantly affect A. Because the moisture content at depth decreases in time during redistribution, it follows that the A parameter also changes with time. Consequently, a method to calculate a representative value of A was developed. When applied to field data, the desorptivity model estimated cumulative evaporation well. The model is easy to calculate, but its usefulness is limited because it requires an independent estimate of the time of transition between the first and second stages of evaporation. The model shows that bulk evaporation after the transition to the second stage is largely independent of climatic conditions.

  6. Adsorption, aggregation, and desorption of proteins on smectite particles.

    Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

    2014-10-07

    We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

  7. Rapid decompression and desorption induced energetic failure in coal

    Shugang Wang

    2015-06-01

    Full Text Available In this study, laboratory experiments are conducted to investigate the rapid decompression and desorption induced energetic failure in coal using a shock tube apparatus. Coal specimens are recovered from Colorado at a depth of 610 m. The coal specimens are saturated with the strong sorbing gas CO2 for a certain period and then the rupture disc is suddenly broken on top of the shock tube to generate a shock wave propagating upwards and a rarefaction wave propagating downwards through the specimen. This rapid decompression and desorption has the potential to cause energetic fragmentation in coal. Three types of behaviors in coal after rapid decompression are found, i.e. degassing without fragmentation, horizontal fragmentation, and vertical fragmentation. We speculate that the characteristics of fracture network (e.g. aperture, spacing, orientation and stiffness and gas desorption play a role in this dynamic event as coal can be considered as a dual porosity, dual permeability, dual stiffness sorbing medium. This study has important implications in understanding energetic failure process in underground coal mines such as coal gas outbursts.

  8. Effect of equilibration time on Pu desorption from goethite

    Wong, Jennifer C.; Powell, Brian A.; Zavarin, Mavrik; Begg, James D.; Kersting, Annie B.

    2015-01-01

    It has been suggested that strongly sorbing ions such as plutonium may become irreversibly bound to mineral surfaces over time which has implications for near- and far-field transport of Pu. Batch adsorption-desorption data were collected as a function of time and pH to study the surface stability of Pu on goethite. Pu(IV) was adsorbed to goethite over the pH range 4.2 to 6.6 for different periods of time (1, 6, 15, 34 and 116 d). Following adsorption, Pu was leached from the mineral surface with desferrioxamine B (DFOB), a complexant capable of effectively competing with the goethite surface for Pu. The amount of Pu desorbed from the goethite was found to vary as a function of the adsorption equilibration time, with less Pu removed from the goethite following longer adsorption periods. This effect was most pronounced at low pH. Logarithmic desorption distribution ratios for each adsorption equilibration time were fit to a pH-dependent model. Model slopes decreased between 1 and 116 d adsorption time, indicating that overall Pu(IV) surface stability on goethite surfaces becomes less dependent on pH with greater adsorption equilibration time. The combination of adsorption and desorption kinetic data suggest that non-redox aging processes affect Pu sorption behavior on goethite.

  9. The Design and Development of Enhanced Thermal Desorption Products

    R. Humble

    2005-01-01

    Full Text Available This research study is based on a knowledge-transfer collaboration between The National Centre for Product Design and Development Research (PDR and Markes International Ltd. The aim of the two-year collaboration has been to implement design tools and techniques for the development of enhanced thermal desorption products. Thermal desorption is a highly-specialised technique for the analysis of trace-level volatile organic compounds. This technique allows minute quantities of these compounds to be measured; however, there is an increasing demand from customers for greater sensitivity over a wider range of applications, which means new design methodologies need to be evaluated. The thermal desorption process combines a number of disparate chemical, thermal and mechanical disciplines, and the major design constraints arise from the need to cycle the sample through extremes in temperature. Following the implementation of a comprehensive product design specification, detailed design solutions have been developed using the latest 3D CAD techniques. The impact of the advanced design techniques is assessed in terms of improved product performance and reduced development times, and the wider implications of new product development within small companies are highlighted.  

  10. A systematic neutron reflectometry study on hydrogen absorption in thin Mg{sub 1-x}Al{sub x} alloy films

    Fritzsche, H.; Poirier, E. [National Research Council of Canada, Chalk River, ON (Canada). Canadian Neutron Beam Centre; Haagsma, J.; Ophus, C.; Luber, E.; Harrower, C.T.; Mitlin, D. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering; National Research Council of Canada, Edmonton, AB (Canada). National Inst. for Nanotechnology

    2010-10-15

    Various methods for storing hydrogen have been examined in an effort to find ways to store hydrogen in increasingly smaller volumes with decreasing weight of the whole hydrogen storage system. Metal hydrides, in which hydrogen is chemically bound to a metal atom, are considered to be very promising candidates for hydrogen storage because they have high gravimetric and volumetric storage capacities. This study investigated the effect of different magnesium (Mg) and aluminium (Al) ratios on the absorption and desorption properties of thin films. Neutron reflectometry (NR) was used in this study to better understand the absorption and desorption properties of commercially promising hydrogen storage materials. The large negative scattering length of hydrogen atoms changes the reflectivity curve substantially, so that NR can determine the total amount of stored hydrogen as well as the hydrogen distribution along the film normal, with nanometer resolution. In order to use NR, the samples must have smooth surfaces, and the film thickness should range between 10 and 200 nm. Thin Mg{sub 1-x}Al{sub x} alloy films (x = 0.2, 0.3, 0.4, 0.67) capped with a palladium (Pd) catalyst layer were used in this study. The NR experiments revealed that Mg{sub 0.7}Al{sub 0.3} is the optimum composition for this binary alloy system, with the highest amount of stored hydrogen and the lowest desorption temperature. All the thin films expanded by approximately 20 percent due to hydrogen absorption. The hydrogen was stored only in the MgAl layer without any hydrogen in the Pd layer. It was concluded that NR can be used to effectively determine the hydrogen profile in thin MgAl films. 29 refs., 5 figs.

  11. Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

    Fossing, H.

    1992-01-01

    Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

  12. Investigations on ion-beam induced desorption from cryogenic surfaces; Untersuchungen zu ionenstrahlinduzierter Desorption von kryogenen Oberflaechen

    Maurer, Christoph

    2017-07-03

    A central component of FAIR, the Facility for Antiproton and Ion Research, will be the superconducting heavy ion synchrotron SIS100, which is supposed to provide reliable, high intensity beams for various applications. Its beam intensity is governed by the space charge limit, while the maximum energy is determined by the machine's magnetic rigidity. That means, ions with higher charge state can be accelerated to a higher energy, but with less intensity. For highest intensity beams, intermediate charge states have to be used instead of high charge state ions. This alleviates the issue of space charge but gives rise to dynamic vacuum effects, which also limit beam intensity: beam particles collide with residual gas particles, which leads to charge exchange and their subsequent loss. Impacting on the chamber wall, these ions release adsorbed gas particles. This process is called desorption and leads to a localized increase in pressure, which in turn causes more charge exchange. After a few rounds of self amplification, this can lead to total beam loss. This ''runaway-desorption'' is typically the main beam intensity limiting process for intermediate charge state (heavy) ion beams. The extent of this phenomenon is governed by two factors: the initial beam intensity and the desorption yield. The latter is examined within the scope of this thesis. Special emphasis is placed on the influence of the target's temperature, since the SIS100 will be a superconducting machine with cryogenic vacuum chamber walls. In order to investigate this topic, an experimental setup has been devised, built at the SIS18 and taken into commission. Based on the experience gained during operation, it has been continuously improved and extended. Another central innovation presented in this thesis is the use of gas dynamics simulations for an improved method of data analysis. Using this technique, environmental conditions like the chamber geometry and the connected

  13. Desorption of Benzene, 1,3,5-Trifluorobenzene, and Hexafluorobenzene from a Graphene Surface: The Effect of Lateral Interactions on the Desorption Kinetics.

    Smith, R Scott; Kay, Bruce D

    2018-05-03

    The desorption of benzene, 1,3,5-trifluorobenzene (TFB), and hexafluorobenzene (HFB) from a graphene covered Pt(111) substrate was investigated using temperature programmed desorption (TPD). All three species have well resolved monolayer and second layer desorption peaks. The desorption spectra for submonolayer coverages of benzene and hexafluorobenzene are consistent with first order desorption kinetics. In contrast, the submonolayer TPD spectra for 1,3,5-trifluorobenzene align on a common leading-edge which is indicative of zero order desorption kinetics. The desorption behavior of the three molecules can be correlated with the strength of the quadrupole moments. Calculations (second-order Møller-Plesset perturbation and density functional theory) show that the potential minimum for coplanar TFB dimers is more than a factor of two greater than that for either benzene or HFB dimers. The calculations support the interpretation that benzene and HFB are less likely to form the two dimensional islands that are needed for submonolayer zero order desorption kinetics.

  14. Electron stimulated molecular desorption of a non-evaporable Zr-V-Fe alloy getter at room temperature

    Le Pimpec, Frederic; Laurent, Jean Michel

    2002-01-01

    Electron stimulated molecular desorption (ESD) from a non-evaporable getters (NEG) St 707 registered trademark (SAES Getters trademark ) sample after conditioning and after saturation with isotopic carbon monoxide (cf. nomenclature in Handbook of Chemistry and Physics, CRC Press, 1994), **1**3C**1**8O, has been studied on a laboratory setup. Measurements were performed using an electron beam of 300 eV kinetic energy, with an average electron intensity of 1.6 multiplied by 10**1**5 electrons s**-**1. The electrons were impinging on the 15 cm **2 target surface at perpendicular incidence. It is found that the desorption yields eta (molecules/electron) of the characteristic gases in an UHV system (hydrogen, methane, water, carbon monoxide, carbon dioxide) for a fully activated NEG as well as for a NEG fully saturated with **1**3C**1**8O are lower than for OFHC copper baked at 120 degree C. A small fraction only of the gas which is required to saturate the getter surface can be re-desorbed and thus appears to be ...

  15. Sorption/Desorption Behavior and Mechanism of NH4(+) by Biochar as a Nitrogen Fertilizer Sustained-Release Material.

    Cai, Yanxue; Qi, Hejinyan; Liu, Yujia; He, Xiaowei

    2016-06-22

    Biochar, the pyrolysis product of biomass material with limited oxygen, has the potential to increase crop production and sustained-release fertilizer, but the understanding of the reason for improving soil fertility is insufficient, especially the behavior and mechanism of ammonium sulfate. In this study, the sorption/desorption effect of NH4(+) by biochar deriving from common agricultural wastes under different preparation temperatures from 200 to 500 °C was studied and its mechanism was discussed. The results showed that biochar displayed excellent retention ability in holding NH4(+) above 90% after 21 days under 200 °C preparation temperature, and it can be deduced that the oxygen functional groups, such as carboxyl and keto group, played the primary role in adsorbing NH4(+) due to hydrogen bonding and electrostatic interaction. The sorption/desorption effect and mechanism were studied for providing an optional way to dispose of agricultural residues into biochar as a nitrogen fertilizer sustained-release material under suitable preparation temperature.

  16. Retention of hydrogen isotopes and helium in nickel

    Okada, Mitsumasa; Sato, Rikiya; Yamaguchi, Kenji; Yamawaki, Michio [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab.

    1996-10-01

    In the present study, a thin foil of nickel was irradiated by H{sub 2}{sup +}, D{sub 2}{sup +} and He{sup +} to a fluence of 1.2-6.0x10{sup 20}/m{sup 2} using the TBTS (Tritium Beam Test System) apparatus. The thermal desorption spectroscopy (TDS) technique was employed to evaluate the total amount of retained hydrogen isotope and helium atoms in nickel. In the spectra, two peaks appeared at 440-585K and 720-735K for helium. Hydrogen isotopes irradiation after helium preirradiation were found to enhance the helium release and to decrease the peak temperatures. Helium irradiation after hydrogen isotopes preirradiation were found to enhance the helium release, but the peak temperature showed little difference from that without preirradiation. (author)

  17. Plasma-surface interaction in negative hydrogen ion sources

    Wada, Motoi

    2018-05-01

    A negative hydrogen ion source delivers more beam current when Cs is introduced to the discharge, but a continuous operation of the source reduces the beam current until more Cs is added to the source. This behavior can be explained by adsorption and ion induced desorption of Cs atoms on the plasma grid surface of the ion source. The interaction between the ion source plasma and the plasma grid surface of a negative hydrogen ion source is discussed in correlation to the Cs consumption of the ion source. The results show that operation with deuterium instead of hydrogen should require more Cs consumption and the presence of medium mass impurities as well as ions of the source wall materials in the arc discharge enlarges the Cs removal rate during an ion source discharge.

  18. Hydrogen retention behavior of beryllides as advanced neutron multipliers

    Y. Fujii

    2016-12-01

    Full Text Available Beryllium intermetallic compounds (beryllides are the most promising candidate materials for use as advanced neutron multipliers in future fusion reactors because of their low swelling and high stability at high temperatures. Recently, beryllium–titanium beryllide pebbles such as Be12Ti have been successfully fabricated using a novel granulation process. In this study, the fundamental aspects of the behavior of hydrogen isotopes in Be12Ti pebbles were investigated via thermal desorption spectroscopy and transmission electron microscopy. In addition, atomistic calculations using first principles electronic-structure methods were applied to determine the solution energy of hydrogen in Be12Ti. The results showed simpler and weaker hydrogen-trapping efficiency for Be12Ti than for pure Be.

  19. Hydrogen evolution on Au(111) covered with submonolayers of Pd

    Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan

    2011-01-01

    A theoretical investigation of electrochemical hydrogen evolution on Au(111) covered with submonolayers of Pd is presented. The size and shape of monoatomically high Pd islands formed on the Au(111) surface are determined using Monte Carlo simulations, for Pd coverages varying from 0.02 to 0.95 ML....... The energetics of adsorption and desorption of hydrogen on/from different types of sites on the Pd-Au(111) surface are assessed by means of density functional theory calculations combined with thermodynamic modeling. Based on the density functional and Monte Carlo data, the hydrogen evolution activity...... is evaluated with a micro-kinetic model. The analysis reproduces measured Pd-coverage-dependent activities for Pd submonolayers exceeding similar to 0.15 ML and enables the relative contributions from different types of electrocatalytically active sites to be determined. Finally, the implications of surface...

  20. Extraction and determination of hydrogen in uranium and zirconium

    Champeix, L.; Coblence, G.; Darras, R.

    1959-01-01

    The method of desorption under vacuum at high temperatures in the solid phase, which gives good results in the case of steels, has been applied to uranium and zirconium. In these two metals hydrogen is found mainly in the form of hydride. It is chiefly a question of determining the most suitable temperature and the heating time necessary to obtain an almost total extraction of hydrogen. Two considerations must be taken into account in the choice of temperature. It should be such that on the one hand the hydride decomposes rapidly and completely at the reduced pressure applied, and on the other hand the diffusion of hydrogen through the metal takes place fairly quickly. The apparatus and the method used are described; systematic tests have led to the adoption of temperatures of 650 deg. C for uranium and 1050 deg. C for zirconium. (author) [fr

  1. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma

    Barbier, G.

    1997-01-01

    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author)

  2. Hydrogen behaviour study in plasma facing a-C:H and a-SiC:H hydrogenated amorphous materials for fusion reactors

    Barbier, Gauzelin

    1997-01-01

    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. Firstly, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce this interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a-SiC:H substrate can be benefit in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a -SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a-C:H and a-SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modeling of hydrogen diffusion under irradiation has been also proposed. (author)

  3. Hydrogen production through microheterogeneous photocatalysis of hydrogen sulfide cleavage. The thiosulfate cycle

    Borgarello, E; Serpone, N; Graetzel, M; Pelizzetti, E

    1985-01-01

    Cleavage of hydrogen sulfide into hydrogen and sulfur occurs in alkaline aqueous CdS dispersions under visible light illumination. Small quantities of a noble metal catalyst (RuO/sub 2/) loaded onto 'naked' CdS particles markedly improve the yield of hydrogen formation. The effect of RuO/sub 2/ is ascribed to catalysis of electron transfer to proton. Simultaneous and efficient photogeneration of hydrogen and thiosulfate occurs in CdS dispersions containing both sulfite and bisulfide (or sulfide) ions. Electron transfer from the conduction band of CdS to that of TiO/sub 2/ particles occurs in alkaline suspensions containing these HS/sup -/ ions and has been exploited to improve the performance of a system achieving decomposition of H/sub 2/S by visible light. Equally important is a recent finding that the performance of a system containing 'naked' CdS in combination with RuO/sub 2/-loaded TiO/sub 2/ particles is far better than that of CdS/RuO/sub 2/ alone. Additionally, conduction band electrons produced by bandgap excitation of TiO/sub 2/ particles efficiently reduce thiosulfate to sulfide and sulfite. The valence band process in alklaine TiO/sub 2/ dispersions is thought to involve oxidation of S/sub 2/O/sub 3//sup 2 -/ to tetrathionate, S/sub 4/O/sub 6//sup 2 -/, which quantitatively dismutates into sulfite and thiosulfate. The photodriven disproportionation of thiosulfate into sulfide and sulfate is of great interest in systems that photochemically cleave hydrogen sulfide into hydrogen and sulfur. (author).

  4. Multiscale modelling of hydrogen behaviour on beryllium (0001 surface

    Ch. Stihl

    2016-12-01

    Full Text Available Beryllium is proposed to be a neutron multiplier and plasma facing material in future fusion devices. Therefore, it is crucial to acquire an understanding of the microscopic mechanisms of tritium accumulation and release as a result of transmutation processes that Be undergoes under neutron irradiation. A multiscale simulation of ad- and desorption of hydrogen isotopes on the beryllium (0001 surface is developed. It consists of ab initio calculations of certain H adsorption configurations, a suitable cluster expansion approximating the energies of arbitrary configurations, and a kinetic Monte Carlo method for dynamic simulations of adsorption and desorption. The processes implemented in the kinetic Monte Carlo simulation are deduced from further ab initio calculations comprising both, static relaxation as well as molecular dynamics runs. The simulation is used to reproduce experimental data and the results are compared and discussed. Based on the observed results, proposals for a refined model are made.

  5. Hydrogen converters

    Mondino, Angel V.

    2003-01-01

    The National Atomic Energy Commission of Argentina developed a process of 99 Mo production from fission, based on irradiation of uranium aluminide targets with thermal neutrons in the RA-3 reactor of the Ezeiza Atomic Centre. These targets are afterwards dissolved in an alkaline solution, with the consequent liberation of hydrogen as the main gaseous residue. This work deals with the use of a first model of metallic converter and a later prototype of glass converter at laboratory scale, adjusted to the requirements and conditions of the specific redox process. Oxidized copper wires were used, which were reduced to elementary copper at 400 C degrees and then regenerated by oxidation with hot air. Details of the bed structure and the operation conditions are also provided. The equipment required for the assembling in cells is minimal and, taking into account the operation final temperature and the purge with nitrogen, the procedure is totally safe. Finally, the results are extrapolated for the design of a converter to be used in a hot cell. (author)

  6. Desorption Kinetics and Mechanisms of CO2 on Amine-Based Mesoporous Silica Materials

    Yang Teng

    2017-01-01

    Full Text Available Tetraethylenepentamine (TEPA-based mesoporous MCM-41 is used as the adsorbent to determine the CO2 desorption kinetics of amine-modified materials after adsorption. The experimental data of CO2 desorption as a function of time are derived by zero-length column at different temperatures (35, 50, and 70 °C and analyzed by Avrami’s fractional-order kinetic model. A new method is used to distinguish the physical desorption and chemical desorption performance of surface-modified mesoporous MCM-41. The activation energy Ea of CO2 physical desorption and chemical desorption calculated from Arrhenius equation are 15.86 kJ/mol and 57.15 kJ/mol, respectively. Furthermore, intraparticle diffusion and Boyd’s film models are selected to investigate the mechanism of CO2 desorption from MCM-41 and surface-modified MCM-41. For MCM-41, there are three rate-limiting steps during the desorption process. Film diffusion is more prominent for the CO2 desorption rates at low temperatures, and pore diffusion mainly governs the rate-limiting process under higher temperatures. Besides the surface reaction, the desorption process contains four rate-limiting steps on surface-modified MCM-41.

  7. Real-time detection of sub-monolayer desorption phenomena during electrochemical reactions: Instrument development and applications

    Trimarco, Daniel Bøndergaard

    , making it highly suitable for electrochemistry studies. Incorporating the membrane chip into a stagnant thin-layer electrochemistry cell, 100% collection efficiency is ensured, which makes it possible to utilize the full dynamic range of a standard MS, and thereby analyze desorption phenomena during...... are made possible by the transient and steady-state introduction CO reactant gas, respectively, through the membrane. A mass transport model is used to describe the analytetransport from the surface of an electrode, through the stagnant thin-layer cell, through the membrane chip and into the mass...... reaction pathway towards methane production is temporarily established. The phenomenon is shown only to affect the formation of methane, leaving ethylene and hydrogen formation unaffected. Using density functional theory (DFT) it is demonstrated that adsorbed oxygen on surface sites adjacent...

  8. Quantum dots assisted laser desorption/ionization mass spectrometric detection of carbohydrates: qualitative and quantitative analysis.

    Bibi, Aisha; Ju, Huangxian

    2016-04-01

    A quantum dots (QDs) assisted laser desorption/ionization mass spectrometric (QDA-LDI-MS) strategy was proposed for qualitative and quantitative analysis of a series of carbohydrates. The adsorption of carbohydrates on the modified surface of different QDs as the matrices depended mainly on the formation of hydrogen bonding, which led to higher MS intensity than those with conventional organic matrix. The effects of QDs concentration and sample preparation method were explored for improving the selective ionization process and the detection sensitivity. The proposed approach offered a new dimension to the application of QDs as matrices for MALDI-MS research of carbohydrates. It could be used for quantitative measurement of glucose concentration in human serum with good performance. The QDs served as a matrix showed the advantages of low background, higher sensitivity, convenient sample preparation and excellent stability under vacuum. The QDs assisted LDI-MS approach has promising application to the analysis of carbohydrates in complex biological samples. Copyright © 2016 John Wiley & Sons, Ltd.

  9. Field desorption mass spectroscopy monitoring of changes in hydrocarbon type composition during petroleum biodegradation

    Huesemann, M.H.

    1995-01-01

    A comprehensive petroleum hydrocarbon characterization procedure involving group type separation, boiling point distribution, and hydrocarbon typing by field desorption mass spectroscopy (FDMS) has been developed to quantify changes in hydrocarbon type composition during bioremediation of petroleum-contaminated soils. FDMS is able to quantify the concentration of hundreds of specific hydrocarbon types based on their respective hydrogen deficiency (z-number) and molecular weight (carbon number). Analytical results from two bioremediation experiments involving soil contaminated with crude oil and motor oil indicate that alkanes and two-ring saturates (naphthenes) were readily biodegradable. In addition, low-molecular-weight hydrocarbons generally were biodegraded to a larger extent than those of high molecular weight. More importantly, it was found that the extent of biodegradation of specific hydrocarbon types was comparable between treatments and appeared to be unaffected by the petroleum contaminant source, soil type, or experimental conditions. It was therefore concluded that in these studies the extent of total petroleum hydrocarbon (TPH) biodegradation is primarily affected by the molecular composition of the petroleum hydrocarbons present in the contaminated soil

  10. Hydrogen embrittlement property of a 1700-MPa-class ultrahigh-strength tempered martensitic steel

    Li Songjie; Zhang Boping [School of Materials Science and Engineering, University of Science and Technology Beijing, No. 30 Xueyuan Road, Hidian Zone, Beijing 100083 (China); Akiyama, Eiji; Yuuji, Kimura; Tsuzaki, Kaneaki [Structural Metals Center, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Uno, Nobuyoshi, E-mail: AKIYAMA.Eiji@nims.go.j [Nippon Steel and Sumikin Metal Products Co, Ltd, SA Bldg., 17-12 Kiba 2-chome, Koto-ku, Tokyo (Japan)

    2010-04-15

    The hydrogen embrittlement property of a prototype 1700-MPa-class ultrahigh-strength steel (NIMS17) containing hydrogen traps was evaluated using a slow strain rate test (SSRT) after cathodic hydrogen precharging, cyclic corrosion test (CCT) and atmospheric exposure. The hydrogen content in a fractured specimen was measured after SSRT by thermal desorption spectroscopy (TDS). The relationship between fracture stress and hydrogen content for the hydrogen-precharged specimens showed that the fracture stress of NIMS17 steel was higher, at a given hydrogen content, than that of conventional AISI 4135 steels with tensile strengths of 1300 and 1500 MPa. This suggests better resistance of NIMS17 steel to hydrogen embrittlement. However, hydrogen uptake to NIMS17 steel under CCT and atmospheric exposure decreased the fracture stress. This is because of the stronger hydrogen uptake to the steel containing hydrogen traps than to the AISI 4135 steels. Although NIMS17 steel has a higher strength level than AISI 4135 steel with a tensile strength of 1500 MPa, the decrease in fracture stress is similar between these steels.

  11. Hydrogen embrittlement property of a 1700-MPa-class ultrahigh-strength tempered martensitic steel

    Songjie Li, Eiji Akiyama, Kimura Yuuji, Kaneaki Tsuzaki, Nobuyoshi Uno and Boping Zhang

    2010-01-01

    Full Text Available The hydrogen embrittlement property of a prototype 1700-MPa-class ultrahigh-strength steel (NIMS17 containing hydrogen traps was evaluated using a slow strain rate test (SSRT after cathodic hydrogen precharging, cyclic corrosion test (CCT and atmospheric exposure. The hydrogen content in a fractured specimen was measured after SSRT by thermal desorption spectroscopy (TDS. The relationship between fracture stress and hydrogen content for the hydrogen-precharged specimens showed that the fracture stress of NIMS17 steel was higher, at a given hydrogen content, than that of conventional AISI 4135 steels with tensile strengths of 1300 and 1500 MPa. This suggests better resistance of NIMS17 steel to hydrogen embrittlement. However, hydrogen uptake to NIMS17 steel under CCT and atmospheric exposure decreased the fracture stress. This is because of the stronger hydrogen uptake to the steel containing hydrogen traps than to the AISI 4135 steels. Although NIMS17 steel has a higher strength level than AISI 4135 steel with a tensile strength of 1500 MPa, the decrease in fracture stress is similar between these steels.

  12. Hydrogen embrittlement property of a 1700-MPa-class ultrahigh-strength tempered martensitic steel

    Li Songjie; Zhang Boping; Akiyama, Eiji; Yuuji, Kimura; Tsuzaki, Kaneaki; Uno, Nobuyoshi

    2010-01-01

    The hydrogen embrittlement property of a prototype 1700-MPa-class ultrahigh-strength steel (NIMS17) containing hydrogen traps was evaluated using a slow strain rate test (SSRT) after cathodic hydrogen precharging, cyclic corrosion test (CCT) and atmospheric exposure. The hydrogen content in a fractured specimen was measured after SSRT by thermal desorption spectroscopy (TDS). The relationship between fracture stress and hydrogen content for the hydrogen-precharged specimens showed that the fracture stress of NIMS17 steel was higher, at a given hydrogen content, than that of conventional AISI 4135 steels with tensile strengths of 1300 and 1500 MPa. This suggests better resistance of NIMS17 steel to hydrogen embrittlement. However, hydrogen uptake to NIMS17 steel under CCT and atmospheric exposure decreased the fracture stress. This is because of the stronger hydrogen uptake to the steel containing hydrogen traps than to the AISI 4135 steels. Although NIMS17 steel has a higher strength level than AISI 4135 steel with a tensile strength of 1500 MPa, the decrease in fracture stress is similar between these steels.

  13. Nickel foam/polyaniline-based carbon/palladium composite electrodes for hydrogen storage

    Skowronski, Jan M.; Urbaniak, Jan

    2008-01-01

    The sandwich-like nickel/palladium/carbon electrodes exhibiting ability to absorb hydrogen in alkaline solution are presented. Electrodes were prepared by successive deposition of palladium and polyaniline layers on nickel foam substrate followed by heat treatment to give Ni/Pd/C electrode. It was shown that thermal conversion of polymer into carbon layer and subsequent thermal activation of carbon component bring about the modification of the mechanism of reversible hydrogen sorption. It was proven that carbon layer, interacting with Pd catalyst, plays a considerable role in the process of hydrogen storage. In the other series of experiments, Pd particles were dispersed electrochemically on carbon coating leading to Ni/C/Pd system. The adding of the next carbon layer resulted in Ni/C/Pd/C electrodes. Electrochemical properties of the electrodes depend on both the sequence of Pd and C layers and the preparation/activation of carbon coating. Electrochemical behavior of sandwich-like electrodes in the reaction of hydrogen sorption/desorption was characterized in 6 M KOH using the cyclic voltammetry method and the results obtained were compared to those for Ni/Pd electrode. The anodic desorption of hydrogen from electrodes free and containing carbon layer was considered after the potentiodynamic as well as potentiostatic sorption of hydrogen. The influence of the sorption potential and the time of rest of electrodes at a cut-off circuit on the kinetics of hydrogen recovery were examined. The results obtained for Ni/Pd/C electrodes indicate that the displacement of hydrogen between C and Pd phase takes place during the rest at a cut-off circuit. Electrodes containing carbon layer require longer time for hydrogen electrosorption. On the other hand, the presence of carbon layer in electrodes is advantageous because a considerable longer retention of hydrogen is possible, as compared to Pd/Ni electrode. Hydrogen stored in sandwich-like electrodes can instantly be

  14. S187. SEARCHING FOR BRAIN CO-EXPRESSION MODULES THAT CONTRIBUTE DISPROPORTIONATELY TO THE COMMON POLYGENIC RISK FOR SCHIZOPHRENIA

    Costas, Javier; Paramo, Mario; Arrojo, Manuel

    2018-01-01

    Abstract Background Genomic research has revealed that schizophrenia is a highly polygenic disease. Recent estimates indicate that at least 71% of genomic segments of 1 Mb include one or more risk loci for schizophrenia (Loh et al., Nature Genet 2015). This extremely high polygenicity represents a challenge to decipher the biological basis of schizophrenia, as it is expected that any set of SNPs with enough size will be associated with the disorder. Among the different gene sets available for study (such as those from Gene Ontology, KEGG pathway, Reactome pathways or protein protein interaction datasets), those based on brain co-expression networks represent putative functional relationships in the relevant tissue. The aim of this work was to identify brain co-expression networks that contribute disproportionately to the common polygenic risk for schizophrenia to get more insight on schizophrenia etiopathology. Methods We analyzed a case -control dataset consisting of 582 schizophrenia patients from Galicia, NW Spain, and 591 ancestrally matched controls, genotyped with the Illumina PsychArray. Using as discovery sample the summary results from the largest GWAS of schizophrenia to date (Psychiatric Genomics Consortium, SCZ2), we generated polygenic risk scores (PRS) in our sample based on SNPs located at genes belonging to brain co-expression modules determined by the CommonMind Consortium (Fromer et al., Nature Neurosci 2016). PRS were generated using the clumping procedure of PLINK, considering several different thresholds to select SNPs from the discovery sample. In order to test if any specific module increased risk to schizophrenia more than expected by their size, we generated up to 10,000 random permutations of the same number of SNPs, matched by frequency, distance to nearest gene, number of SNPs in LD and gene density, using SNPsnap. Results As expected, most modules with enough number of independent SNPs belonging to them showed a significant increase in

  15. Electric arc hydrogen heaters

    Zasypin, I.M.

    2000-01-01

    The experimental data on the electric arc burning in hydrogen are presented. Empirical and semiempirical dependences for calculating the arc characteristics are derived. An engineering method of calculating plasma torches for hydrogen heating is proposed. A model of interaction of a hydrogen arc with a gas flow is outlined. The characteristics of plasma torches for heating hydrogen and hydrogen-bearing gases are described. (author)

  16. Hydrogen storage in Mg-Ni-Fe compounds prepared by melt spinning and ball milling

    Palade, P. [Settore Materiali, Dipartimento di Ingegneria Meccanica, Universita di Padova, via Marzolo 9, 35131 Padova (Italy); National Institute for Physics of Materials, Atomistilor 105 bis, P.O. Box MG-7, 077125 Bucharest-Magurele (Romania); Sartori, S. [Settore Materiali, Dipartimento di Ingegneria Meccanica, Universita di Padova, via Marzolo 9, 35131 Padova (Italy); Maddalena, A. [Settore Materiali, Dipartimento di Ingegneria Meccanica, Universita di Padova, via Marzolo 9, 35131 Padova (Italy); Principi, G. [Settore Materiali, Dipartimento di Ingegneria Meccanica, Universita di Padova, via Marzolo 9, 35131 Padova (Italy)]. E-mail: giovanni.principi@unipd.it; Lo Russo, S. [Dipartimento di Fisica, Universita di Padova, Via Marzolo 8, 35131 Padova (Italy); Lazarescu, M. [National Institute for Physics of Materials, Atomistilor 105 bis, P.O. Box MG-7, 077125 Bucharest-Magurele (Romania); Schinteie, G. [National Institute for Physics of Materials, Atomistilor 105 bis, P.O. Box MG-7, 077125 Bucharest-Magurele (Romania); Kuncser, V. [National Institute for Physics of Materials, Atomistilor 105 bis, P.O. Box MG-7, 077125 Bucharest-Magurele (Romania); Filoti, G. [National Institute for Physics of Materials, Atomistilor 105 bis, P.O. Box MG-7, 077125 Bucharest-Magurele (Romania)

    2006-05-18

    Magnesium-rich Mg-Ni-Fe intermetallic compounds have been prepared by two different routes: (a) short time ball milling of ribbons obtained by melt spinning; (b) long time ball milling of a mixture of MgH{sub 2}, Ni and Fe powders. The first type of samples displays an hydrogen desorption kinetics better than the second one. Pressure composition isotherm measurements exhibit for both type of samples two plateaux, the lower and wider corresponding to the MgH{sub 2} phase and the upper and shorter corresponding to the Mg{sub 2}NiH{sub 4} phase. The presence of the two types of hydrides is confirmed by X-ray diffraction analysis. Moessbauer spectroscopy shows that in melt spun and subsequently milled samples iron is mainly in a disordered structure and segregates after hydrogenation, while in directly milled powders remains mainly unalloyed. After multiple hydrogen absorption/desorption cycles the main part of iron is in metallic state in samples of both types, those of first type preserving better hydrogen desorption kinetics.

  17. Maltooligosaccharide disproportionation reaction

    Albenne, Cécile; Skov, Lars K; Mirza, Osman Asghar

    2002-01-01

    Amylosucrase from Neisseria polysaccharea (AS) is a remarkable transglycosidase of family 13 of the glycoside hydrolases that catalyses the synthesis of an amylose-like polymer from sucrose and is always described as a sucrose-specific enzyme. Here, we demonstrate for the first time the ability o...

  18. Carbon nanotube materials for hydrogen storage

    Dillon, A.C.; Parilla, P.A.; Jones, K.M.; Riker, G.; Heben, M.J. [National Renewable Energy Lab., Golden, CO (United States)

    1998-08-01

    Carbon single-wall nanotubes (SWNTs) are essentially elongated pores of molecular dimensions and are capable of adsorbing hydrogen at relatively high temperatures and low pressures. This behavior is unique to these materials and indicates that SWNTs are the ideal building block for constructing safe, efficient, and high energy density adsorbents for hydrogen storage applications. In past work the authors developed methods for preparing and opening SWNTs, discovered the unique adsorption properties of these new materials, confirmed that hydrogen is stabilized by physical rather than chemical interactions, measured the strength of interaction to be {approximately} 5 times higher than for adsorption on planar graphite, and performed infrared absorption spectroscopy to determine the chemical nature of the surface terminations before, during, and after oxidation. This year the authors have made significant advances in synthesis and characterization of SWNT materials so that they can now prepare gram quantities of high-purity SWNT samples and measure and control the diameter distribution of the tubes by varying key parameters during synthesis. They have also developed methods which purify nanotubes and cut nanotubes into shorter segments. These capabilities provide a means for opening the tubes which were unreactive to the oxidation methods that successfully opened tubes, and offer a path towards organizing nanotube segments to enable high volumetric hydrogen storage densities. They also performed temperature programmed desorption spectroscopy on high purity carbon nanotube material obtained from collaborator Prof. Patrick Bernier and finished construction of a high precision Seivert`s apparatus which will allow the hydrogen pressure-temperature-composition phase diagrams to be evaluated for SWNT materials.

  19. Modelling of hydrogen permeability of membranes for high-purity hydrogen production

    Zaika, Yury V.; Rodchenkova, Natalia I.

    2017-11-01

    High-purity hydrogen is required for clean energy and a variety of chemical technology processes. Different alloys, which may be well-suited for use in gas-separation plants, were investigated by measuring specific hydrogen permeability. One had to estimate the parameters of diffusion and sorption to numerically model the different scenarios and experimental conditions of the material usage (including extreme ones), and identify the limiting factors. This paper presents a nonlinear mathematical model taking into account the dynamics of sorption-desorption processes and reversible capture of diffusing hydrogen by inhomogeneity of the material’s structure, and also modification of the model when the transport rate is high. The results of numerical modelling allow to obtain information about output data sensitivity with respect to variations of the material’s hydrogen permeability parameters. Furthermore, it is possible to analyze the dynamics of concentrations and fluxes that cannot be measured directly. Experimental data for Ta77Nb23 and V85Ni15 alloys were used to test the model. This work is supported by the Russian Foundation for Basic Research (Project No. 15-01-00744).

  20. Catalytic glycerol steam reforming for hydrogen production

    Dan, Monica; Mihet, Maria; Lazar, Mihaela D.

    2015-01-01

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H 2 . In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al 2 O 3 . The catalyst was prepared by wet impregnation method and characterized through different methods: N 2 adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H 2 , CH 4 , CO, CO 2 . The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H 2 O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%

  1. Catalytic glycerol steam reforming for hydrogen production

    Dan, Monica, E-mail: monica.dan@itim-cj.ro; Mihet, Maria, E-mail: maria.mihet@itim-cj.ro; Lazar, Mihaela D., E-mail: diana.lazar@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293 Cluj Napoca (Romania)

    2015-12-23

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H{sub 2}. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al{sub 2}O{sub 3}. The catalyst was prepared by wet impregnation method and characterized through different methods: N{sub 2} adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H{sub 2}, CH{sub 4}, CO, CO{sub 2}. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H{sub 2}O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  2. Glyphosate sorption and desorption in soils with distinct phosphorus levels

    Prata Fábio

    2003-01-01

    Full Text Available The sorption of glyphosate by soils occurs due to the inner sphere complex formation with metals of soil oxides, which are related to the soil phosphate adsorption capacity. The aim of this study was to evaluate the effects of increasing rates of phosphorus on sorption and desorption of glyphosate in three soils with different mineralogical attributes. Soils were a Rhodic Kandiudalf, an Anionic Acrudox and a Typic Humaquept. Soil samples were amended with KH2PO4 at equivalent rates of 0; 1,000; 5,000; 20,000 and 50,000 kg ha-1 of P2O5, which are high from the agricultural point of view, but necessary in order to perform sorption and desorption studies. The experimental design consisted of a completely randomized factorial: 2 soils x 5 phosphorus rates and 3 replicates. For the sorption experiments, five glyphosate solutions were employed (0.42; 0.84; 1.68; 3.36 and 6.72 mg L-1, with a 14C radioactivity of 0.233 kBq mL-1. Four steps of the desorption procedure with CaCl2 0.01 mol L-1 and one extraction with Mehlich 3 were performed only at one concentration (0.84 mol L-1. Soil samples were afterwards biologically oxidized to establish the radioactive balance. Glyphosate competes with phosphorus for specific sorption sites, but this competition becomes important when phosphorus is present at rates higher than 1,000 mg dm-3. Moreover, a small amount of applied glyphosate was extracted (<10%, and the extraction increased with increasing soil phosphorus content.

  3. Glyphosate sorption and desorption in soils with distinct phosphorus levels

    Prata, Fabio; Cardinali, Vanessa Camponez do Brasil; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges; Lavorenti, Arquimedes

    2003-01-01

    The sorption of glyphosate by soils occurs due to the inner sphere complex formation with metals of soil oxides, which are related to the soil phosphate adsorption capacity. The aim of this study was to evaluate the effects of increasing rates of phosphorus on sorption and desorption of glyphosate in three soils with different mineralogical attributes. Soils were a Rhodic Kandiudalf, an Anionic Acrudox and a Typic Humaquept. Soil samples were amended with Kh 2 PO 4 at equivalent rates of 0; 1,000; 5,000; 20,000 and 50,000 kg ha -1 of P 2 O 5 , which are high from the agricultural point of view, but necessary in order to perform sorption and desorption studies. The experimental design consisted of a completely randomized factorial: 2 soils x 5 phosphorus rates and 3 replicates. For the sorption experiments, five glyphosate solutions were employed (0.42; 0.84; 1.68; 3.36 and 6.72 mg L -1 ), with a 14 C radioactivity of 0.233 kBq mL -1 . Four steps of the desorption procedures withCaCl 2 0.01 mol L -1 and one extraction with Mehlich 3 were performed only at one concentration (0.84 mol L -1 ). Soil samples were afterwards biologically oxidized to establish the radioactive balance. Glyphosate competes with phosphorus for specific sorption sites, but this competition becomes important when phosphorus is present at rates higher than 1,000 mg dm -3 . Moreover, a small amount of applied glyphosate was extracted (<10%), and the extraction increased with increasing soil phosphorus content. (author)

  4. Glyphosate sorption and desorption in soils with distinct phosphorus levels

    Prata, Fabio [BIOAGRI Labs., Piracicaba, SP (Brazil). Div. de Quimica. Lab. de Radioquimica; Cardinali, Vanessa Camponez do Brasil; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges [Sao Paulo Univ., Piracicaba, SP (Brazil). Escola Superior de Agricultura Luiz de Queiroz. Dept. de Ciencias Exatas; Lavorenti, Arquimedes [Centro de Energia Nuclear na Agricultura (CENA), Piracicaba, SP (Brazil). Secao de Toxicologia

    2003-03-01

    The sorption of glyphosate by soils occurs due to the inner sphere complex formation with metals of soil oxides, which are related to the soil phosphate adsorption capacity. The aim of this study was to evaluate the effects of increasing rates of phosphorus on sorption and desorption of glyphosate in three soils with different mineralogical attributes. Soils were a Rhodic Kandiudalf, an Anionic Acrudox and a Typic Humaquept. Soil samples were amended with Kh{sub 2}PO{sub 4} at equivalent rates of 0; 1,000; 5,000; 20,000 and 50,000 kg ha{sup -1} of P{sub 2}O{sub 5}, which are high from the agricultural point of view, but necessary in order to perform sorption and desorption studies. The experimental design consisted of a completely randomized factorial: 2 soils x 5 phosphorus rates and 3 replicates. For the sorption experiments, five glyphosate solutions were employed (0.42; 0.84; 1.68; 3.36 and 6.72 mg L{sup -1}), with a {sup 14}C radioactivity of 0.233 kBq mL{sup -1}. Four steps of the desorption procedures withCaCl{sub 2} 0.01 mol L{sup -1} and one extraction with Mehlich 3 were performed only at one concentration (0.84 mol L{sup -1}). Soil samples were afterwards biologically oxidized to establish the radioactive balance. Glyphosate competes with phosphorus for specific sorption sites, but this competition becomes important when phosphorus is present at rates higher than 1,000 mg dm{sup -3}. Moreover, a small amount of applied glyphosate was extracted (<10%), and the extraction increased with increasing soil phosphorus content. (author)

  5. Temperature-programmed desorption for membrane inlet mass spectrometry

    Ketola, R.A.; Grøn, C.; Lauritsen, F.R.

    1998-01-01

    We present a novel technique for analyzing volatile organic compounds in air samples using a solid adsorbent together with temperature-programmed desorption and subsequent detection by membrane inlet mass spectrometry (TPD-MIMS). The new system has the advantage of a fast separation of compounds...... to diffuse through the membrane into the mass spectrometer in a few seconds. In this fashion we could completely separate many similar volatile compounds, for example toluene from xylene and trichloroethene from tetrachloroethene. Typical detection limits were at low or sub-nanogram levels, the dynamic range...

  6. Krypton-85 enrichment by adsorption-desorption process

    Khan, A.A.; Deshingkar, D.S.; Ramarathinam, K.

    1975-01-01

    The use of activated charcoal columns in conjunction with cryogenic distillation system for concentration of krypton-85 in fuel reprocessing process off-gas stream is reported. Dynamic adsorption of krypton on activated charcoals and its subsequent desorption by applying vacuum were studied. The possible reduction in the quantity of carrier gas to be liquified in the cryogenic system by utilising this process has been discussed on the basis of results of laboratory evaluations. The possibility of elimination of air and oxygen to avoid explosion hazards associated with radiolytic formation and concentration of ozone has also been considered. (author)

  7. Nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys

    Tashlykova-Bushkevich, Iya I. [Belarusian State University of Informatics and Radioelectronics, Minsk (Belarus)

    2015-12-31

    The present work summarizes recent progress in the investigation of nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys foils produced at exceptionally high cooling rates. We focus here on the potential of modification of hydrogen desorption kinetics in respect to weak and strong trapping sites that could serve as hydrogen sinks in Al materials. It is shown that it is important to elucidate the surface microstructure of the Al alloy foils at the submicrometer scale because rapidly solidified microstructural features affect hydrogen trapping at nanostructured defects. We discuss the profound influence of solute atoms on hydrogen−lattice defect interactions in the alloys. with emphasis on role of vacancies in hydrogen evolution; both rapidly solidified pure Al and conventionally processed aluminum samples are considered.

  8. Hydrogen isotope distributions and retentions in the inner divertor tile of JT-60U

    Oya, Y. [Radioisotope Center, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan)]. E-mail: yoya@ric.u-tokyo.ac.jp; Hirohata, Y. [Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Tanabe, T. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Shibahara, T. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Kimura, H. [Faculty of Science, Shizuoka University, Shizuoka 422-8529 (Japan); Oyaidzu, M. [Faculty of Science, Shizuoka University, Shizuoka 422-8529 (Japan); Arai, T. [Naka Fusion Establishment, Japan Atomic Energy Research Institute, Naka-machi, Naka-gun, Ibaraki 311-0193 (Japan); Masaki, K. [Naka Fusion Establishment, Japan Atomic Energy Research Institute, Naka-machi, Naka-gun, Ibaraki 311-0193 (Japan); Gotoh, Y. [Naka Fusion Establishment, Japan Atomic Energy Research Institute, Naka-machi, Naka-gun, Ibaraki 311-0193 (Japan); Okuno, K. [Faculty of Science, Shizuoka University, Shizuoka 422-8529 (Japan); Miya, N. [Naka Fusion Establishment, Japan Atomic Energy Research Institute, Naka-machi, Naka-gun, Ibaraki 311-0193 (Japan); Hino, T. [Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Tanaka, S. [Graduate School of Engineering, University of Tokyo, Tokyo 113-8656 (Japan)

    2005-11-15

    Retention profiles of hydrogen and deuterium in graphite tiles placed in the inner divertor region of JT-60U were analyzed by secondary ion mass spectroscopy (SIMS) and thermal desorption spectroscopy (TDS). The difference in hydrogen and deuterium retention behaviour is discussed considering the frequency of the strike-point hit and history of NBI heating power. It was found that most of hydrogen/deuterium was retained in the deposited layers, HH deposition layers/DD deposition layers or co-deposited with carbon. Owing to the higher heating power of DD discharges, the deuterium concentration in the DD deposition layers was much lower than that of hydrogen in the HH deposition layers. On the area showing no deposition, very shallow profile of deuterium dominated hydrogen profile. These results indicate that the tritium retention is strongly influenced by the history of discharge and temperatures. Tritium retention on graphite tiles and deposition layers could be significantly reduced with increasing the operation temperature.

  9. Hydrogen isotope distributions and retentions in the inner divertor tile of JT-60U

    Oya, Y.; Hirohata, Y.; Tanabe, T.; Shibahara, T.; Kimura, H.; Oyaidzu, M.; Arai, T.; Masaki, K.; Gotoh, Y.; Okuno, K.; Miya, N.; Hino, T.; Tanaka, S.

    2005-01-01

    Retention profiles of hydrogen and deuterium in graphite tiles placed in the inner divertor region of JT-60U were analyzed by secondary ion mass spectroscopy (SIMS) and thermal desorption spectroscopy (TDS). The difference in hydrogen and deuterium retention behaviour is discussed considering the frequency of the strike-point hit and history of NBI heating power. It was found that most of hydrogen/deuterium was retained in the deposited layers, HH deposition layers/DD deposition layers or co-deposited with carbon. Owing to the higher heating power of DD discharges, the deuterium concentration in the DD deposition layers was much lower than that of hydrogen in the HH deposition layers. On the area showing no deposition, very shallow profile of deuterium dominated hydrogen profile. These results indicate that the tritium retention is strongly influenced by the history of discharge and temperatures. Tritium retention on graphite tiles and deposition layers could be significantly reduced with increasing the operation temperature

  10. Carbon compound used in hydrogen storage; Compuesto de carbon utilizado en almacenamiento de hidrogeno

    Iturbe G, J L; Lopez M, B E [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2004-07-01

    In the present work it is studied the activated carbon of mineral origin for the sorption of hydrogen. The carbon decreased of particle size by means of the one alloyed mechanical. The time of mill was of 10 hours. The characterization one carries out by scanning electron microscopy and X-ray diffraction. The hydrogen sipped in the carbon material it was determined using the Thermal gravimetric method (TGA). The conditions of hydrogenation went at 10 atm of pressure and ambient temperature during 18 hours. They were also carried out absorption/desorption cycles of hydrogen in the same one system of thermal gravimetric analysis. The results showed percentages of sorption of 2% approximately in the cycles carried out in the system TGA and of 4.5% in weight of hydrogen at pressure of 10 atmospheres and ambient temperature during 18 hours. (Author)

  11. Catalytic para-xylene maximization. Part X: Toluene disproportionation on HF promoted H-ZSM-5 catalysts

    Ahmed K. Aboul-Gheit

    2012-12-01

    Full Text Available H-ZSM-5 zeolite catalysts were doped with 2%, 3% and 4%HF to be used for investigating their activities and selectivities for xylenes production and for para-xylene maximization at temperatures of 300–500 °C via toluene disproportionation. This doping caused pore size modification of the H-ZSM-5 catalyst. The reaction was carried out in a fixed bed flow type reactor. The ratio of produced para-xylene relative to its thermodynamic composition reached as high as 3.29 at 300 °C on the 4%HF doped H-ZSM-5 catalyst although this catalyst possessed the lowest amount of the largest pores (3.0–5.7 nm and the smallest pores (0.4–1.7 nm. The overall activities of the catalysts were decreased with an increase in HF doping because of diffusion restriction. The kinetics of the reaction were simply treated and found to give Ea and ΔS∗ values compatible with the characterization data of the catalysts.

  12. Lower limb lengthening in patients with disproportionate short stature with achondroplasia: a systematic review of the last 20 years.

    Schiedel, Frank; Rödl, Robert

    2012-01-01

    Parents of children suffering from disproportionate short stature due to achondroplasia may wish to have surgical leg lengthening carried out for the child. The aim is not to increase height, but rather to achieve physiological proportions in the body. In a systematic review of the literature on the topic dating from the last 20 years, the surgical approaches used for this purpose were analyzed in accordance with the Preferred reporting items for systematic reviews and meta-analyses (PRISMA) criteria. Twelve studies show that to date, involvement of the child in decision-making at the start of treatment has been expected and that it is recommended from the age of 12. In highly heterogeneous patient groups, with varying factors involved and different techniques being used, lengthening (often by more than 10 cm) is described. High complication rates are reported, with many setbacks often requiring repeat surgery. Using PALEY'S multiplier method, the expected standing height, sitting height, and leg length can be predicted and an individualized treatment approach can be planned and operative procedures could be started in early childhood as PERETTI suggests. As the patients are unable to be involved in decision-making as young children, these data may provide a basis for offering differentiated advice to parents, who usually consult a pediatric orthopedist at a very early stage in the child's life.

  13. UV imaging reveals facial areas that are prone to skin cancer are disproportionately missed during sunscreen application.

    Harry Pratt

    Full Text Available Application of sunscreen is a widely used mechanism for protecting skin from the harmful effects of UV light. However, protection can only be achieved through effective application, and areas that are routinely missed are likely at increased risk of UV damage. Here we sought to determine if specific areas of the face are missed during routine sunscreen application, and whether provision of public health information is sufficient to improve coverage. To investigate this, 57 participants were imaged with a UV sensitive camera before and after sunscreen application: first visit; minimal pre-instruction, second visit; provided with a public health information statement. Images were scored using a custom automated image analysis process designed to identify areas of high UV reflectance, i.e. missed during sunscreen application, and analysed for 5% significance. Analyses revealed eyelid and periorbital regions to be disproportionately missed during routine sunscreen application (median 14% missed in eyelid region vs 7% in rest of face, p<0.01. Provision of health information caused a significant improvement in coverage to eyelid areas in general however, the medial canthal area was still frequently missed. These data reveal that a public health announcement-type intervention could be effective at improving coverage of high risk areas of the face, however high risk areas are likely to remain unprotected therefore other mechanisms of sun protection should be widely promoted such as UV blocking sunglasses.

  14. Malnutrition Affects the Urban-Poor Disproportionately: A Study of Nigerian Urban Children of Different Socio-Economic Statuses

    Chukwunonso E.C.C. Ejike

    2016-09-01

    Full Text Available Income inequality within the same place of residence may impact the nutritional status of children. This study therefore investigated the impact of income inequality on the nutritional status of children living in the same place of residence, using anthropometric tools. Children in four schools (Schools 1–4 within the vicinity of a housing estate in Umuahia, Nigeria, that charge fees making them ‘very affordable’, ‘affordable’, ‘expensive’ and ‘very expensive’, respectively, were recruited for the study. Thinness, overweight and obesity were defined using the Cole et al. reference standards. Thinness was present in 10.4% (13.0% of boys, 7.6% of girls; 20.4% (15.6% of boys, 27.3% of girls; and 0.7% (1.4% of boys, 0.0% of girls of children in Schools 1–3, respectively; but absent in school 4. Only 3.7% (1.4% of boys, 6.1% of girls and 5.6% (6.3% of boys, 4.5% of girls of children in Schools 1 and 2, respectively, were overweight/obese. Conversely, 25.8% (18.9% of boys, 32.5% of girls and 41.6% (38.8% of boys, 45.3% of girls of children in Schools 3 and 4, respectively, were overweight/obese. The urban-poor (School 2 are clearly affected by malnutrition disproportionately.

  15. Desorption of large organic molecules by laser-induced plasmon excitation

    Lee, I.; Callcott, T.A.

    1991-01-01

    Ejection of large organic molecules from surfaces by laser-induced electronic-excited desorption has attracted considerable interest in recent years. In addition to the importance of this effect for fundamental investigations of the ejection process, this desorption technique has been applied to the study of large, fragile molecules by mass spectrometry. In this paper, we present a new method to induce electronic excitation on the metal surface for the desorption of large organic molecules. 3 refs., 3 figs

  16. Desorption of metals from Cetraria islandica (L. Ach. Lichen using solutions simulating acid rain

    Čučulović Ana A.

    2014-01-01

    Full Text Available Desorption of metals K, Al, Ca, Mg, Fe, Ba, Zn, Mn, Cu and Sr from Cetraria islandica (L. with solutions whose composition was similar to that of acid rain, was investigated. Desorption of metals from the lichen was performed by five successive desorption processes. Solution mixtures containing H2SO4, HNO3 and H2SO4-HNO3 were used for desorption. Each solution had three different pH values: 4.61, 5.15 and 5.75, so that the desorptions were performed with nine different solutions successively five times, always using the same solution volume. The investigated metals can be divided into two groups. One group was comprised of K, Ca and Mg, which were desorbed in each of the five desorption processes at all pH values used. The second group included Al, Fe, Zn, Ba, Mn and Sr; these were not desorbed in each individual desorption and not at all pH values, whereas Cu was not desorbed at all under any circumstances. Using the logarithmic dependence of the metal content as a function of the desorption number, it was found that potassium builds two types of links and is connected with weaker links in lichen. Potassium is completely desorbed, 80% in the first desorption, and then gradually in the following desorptions. Other metals are linked with one weaker link (desorption 1-38% and with one very strong link (desorption below the metal detection limit. [Projekat Ministarstva nauke Republike Srbije, br. III43009 i br. ON 172019

  17. Surface Magnetism of Cobalt Nanoislands Controlled by Atomic Hydrogen.

    Park, Jewook; Park, Changwon; Yoon, Mina; Li, An-Ping

    2017-01-11

    Controlling the spin states of the surface and interface is key to spintronic applications of magnetic materials. Here, we report the evolution of surface magnetism of Co nanoislands on Cu(111) upon hydrogen adsorption and desorption with the hope of realizing reversible control of spin-dependent tunneling. Spin-polarized scanning tunneling microscopy reveals three types of hydrogen-induced surface superstructures, 1H-(2 × 2), 2H-(2 × 2), and 6H-(3 × 3), with increasing H coverage. The prominent magnetic surface states of Co, while being preserved at low H coverage, become suppressed as the H coverage level increases, which can then be recovered by H desorption. First-principles calculations reveal the origin of the observed magnetic surface states by capturing the asymmetry between the spin-polarized surface states and identify the role of hydrogen in controlling the magnetic states. Our study offers new insights into the chemical control of magnetism in low-dimensional systems.

  18. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    Wronski, Z.; Varin, R.A.; Chiu, C.; Czujko, T.; Calka, A.

    2007-01-01

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg 2 FeH 6 in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H 2 in a thermally programmed desorption experiment at the range 285-295 o C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the β-MgH 2 hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H 2 in the temperature range 329-340 o C in the differential scanning calorimetry experiment. The formation of MgH 2 was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H x , was formed in a mixture with nanometric MgB 2 . Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB 2

  19. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  20. Why hydrogen; Pourquoi l'hydrogene?

    NONE

    2004-02-01

    The energy consumption increase and the associated environmental risks, led to develop new energy sources. The authors present the potentialities of the hydrogen in this context of energy supply safety. They detail the today market and the perspectives, the energy sources for the hydrogen production (fossils, nuclear and renewable), the hydrogen transport, storage, distribution and conversion, the application domains, the associated risks. (A.L.B.)