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Sample records for temperature programmed desorption

  1. Temperature programmed desorption of a binary gas mixture

    NASA Astrophysics Data System (ADS)

    Zuniga-Hansen, Nayeli; Calbi, M. Mercedes

    2014-03-01

    Temperature programmed desorption (TPD) is an experimental technique that is widely used to determine the adsorption properties of a surface. Many existing theoretical studies have focused on the desorption of a single gas species, but the desorption of binary mixtures is a subject that has been relatively less explored. We perform computer simulations of the thermal desorption of binary gas mixtures using a kinetic Monte Carlo scheme. We start with a simple structure formed by a single line of adsorption sites and two species of adsorbates which bind to the surface with different energies. By varying the initial surface coverage, the particle-particle interactions and the concentration of the different adsorbates, we study the kinetics of desorption of the mixture and compare our results to available experimental data.

  2. Reduction Kinetics of Graphene Oxide Determined by Temperature Programmed Desorption

    NASA Astrophysics Data System (ADS)

    Ventrice, Carl; Clark, Nicholas; Field, Daniel; Geisler, Heike; Jung, Inhwa; Yang, Dongxing; Piner, Richard; Ruoff, Rodney

    2009-10-01

    Graphene oxide, which is an electrical insulator, shows promise for use in several technological applications such as dielectric layers in nanoscale electronic devices or as the active region of chemical sensors. In principle, graphene oxide films could also be used as a precursor for the formation of large-scale graphene films by either thermal or chemical reduction of the graphene oxide. In order to determine the thermal stability and reduction kinetics of graphene oxide, temperature program desorption (TPD) measurements have been performed on multilayer films of graphene oxide deposited on SiO2/Si(100) substrates. The graphene oxide was exfoliated from the graphite oxide source material by slow-stirring in aqueous solution, which produces single-layer platelets with an average lateral size of 10 ?m. From the TPD measurements, it was determined that the decomposition process begins at 80 ^oC. The primary desorption products of the graphene oxide films for temperatures up to 300 ^oC are H2O, CO2, and CO, with only trace amounts of O2 being detected. An activation energy of 1.4 eV/molecule was determined by assuming an Arrhenius dependence for the decomposition process.

  3. Temperature-programmed desorption of tritium loaded into beryllium

    NASA Astrophysics Data System (ADS)

    Chakin, V.; Rolli, R.; Vladimirov, P.; Kurinskiy, P.; Klimenkov, M.; Moeslang, A.; Ryczek, L.; Dorn, C.; Markovsky, A.

    2009-12-01

    The influence of grain size and amount of beryllium oxide BeO on the tritium release characteristics of the S-65H and I-220H beryllium grades was investigated. The beryllium samples were loaded with hydrogen at a temperature of 1123 K for 6 h at a pressure of 4 bar in a gas mixture of molecular protium with 45 wppm tritium. The tritium release measurements were performed using a stepped heating ramp with steps of 50 K in the temperature range of 473-1373 K with a duration of each step of 1 h. Five major release peaks were observed. Interpretations of the nature of the peaks are suggested. In particular, we ascribe the low-temperature peaks (300-723 K) to desorption from the surface and connect the shift of the peak at elevated temperature (900-1000 K) with the enhanced diffusion of hydrogen along grain boundaries. The high temperature peak (1123-1373 K) is attributed to dissociation of beryllium hydroxide Be(OH)2, which is formed on the surface and grain boundaries of a sample in a reaction of hydrogen isotopes with beryllium oxide.

  4. Interactions of phenylglycine with amorphous solid water studied by temperature-programmed desorption and photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Tzvetkov, George; Netzer, Falko P.

    2013-07-01

    Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the interactions of phenylglycine (PheGly) with amorphous solid water (ASW) nanolayers (10-50 ML). First, the adsorption and growth of PheGly layers on an AlOx/NiAl(110) surface have been examined. After that, mixed PheGly-ASW layers have been grown on the alumina surface at 110 K. Alternatively, PheGly molecules (from submonolayer to multilayer coverages) have been deposited on top of the ASW surfaces. In mixed PheGly-ASW nanolayers the PheGly phase displays hydrophobic behavior and accumulates near the surfaces of the films, while top-deposited PheGly wets the ASW films forming closed overlayers at low coverages. H2O desorption from the PheGly-ASW films is strongly influenced by the PheGly molecules, i.e., the crystallization of ASW is partially inhibited in the vicinity of the amino acid and a lower desorption temperature of H2O molecules than from pure ASW layers was detected. Thicker PheGly overlayers on ASW provide a kinetic restriction to H2O desorption from the underlying ASW layers until the PheGly molecules become mobile and develop pathways for water desorption at higher temperatures. The results are discussed with respect to the previously obtained data for glycine-ASW layered systems. It has been demonstrated that the substitution of the hydrogen atom in glycine with a phenyl group does not lead to detectable changes in the pathways of ASW desorption. However, desorption of PheGly differs from the desorption of glycine from the similarly structured glycine-ASW nanolayers. The differences are interpreted in terms of adsorbate-adsorbate and adsorbate-substrate interactions.

  5. Temperature programmed desorption studies of water interactions with Apollo lunar samples 12001 and 72501

    NASA Astrophysics Data System (ADS)

    Poston, Michael J.; Grieves, Gregory A.; Aleksandrov, Alexandr B.; Hibbitts, Charles A.; Dyar, M. Darby; Orlando, Thomas M.

    2015-07-01

    The desorption activation energies for water molecules chemisorbed on Apollo lunar samples 72501 (highlands soil) and 12001 (mare soil) were determined by temperature programmed desorption experiments in ultra-high vacuum. A significant difference in both the energies and abundance of chemisorption sites was observed, with 72501 retaining up to 40 times more water (by mass) and with much stronger adsorption interactions, possibly approaching 1.5 eV. The dramatic difference between the samples may be due to differences in mineralogy and surface exposure age. The distribution function of water desorption activation energies for sample 72501 was used as an initial condition to simulate water persistence through a temperature profile matching the lunar day.

  6. Design and construction of a semiautomatic temperature programmed desorption apparatus for ultrahigh vacuum

    NASA Astrophysics Data System (ADS)

    Kondratyuk, Petro; Yates, John T.

    2005-01-01

    A computer-controlled system that allows acquisition of large volumes of temperature programmed desorption data under ultrahigh vacuum conditions has been designed and tested. The vacuum part of the system consists of a sample mounted on a rotation-translation manipulator, a shielded quadrupole mass spectrometer for the desorption flux measurement, and a collimated molecular beam doser for adsorbate delivery. The experiment involves a series of tasks: (1) dosing of the adsorbate onto the surface; (2) calibration of the mass spectrometer gain; (3) translating the dosed sample to the mass spectrometer position; (4) linearly ramping the temperature of the sample to acquire the desorption spectrum; and (5) cooling the sample. In the system described here, these tasks are accomplished automatically. As a result, the time needed for the experiment and the potential for operator errors are substantially reduced. The performance of the system is demonstrated for CCl4 adsorbed on gold-supported single wall carbon nanotubes.

  7. Analyte separation utilizing temperature programmed desorption of a preconcentrator mesh

    DOEpatents

    Linker, Kevin L. (Albuquerque, NM); Bouchier, Frank A. (Albuquerque, NM); Theisen, Lisa (Albuquerque, NM); Arakaki, Lester H. (Edgewood, NM)

    2007-11-27

    A method and system for controllably releasing contaminants from a contaminated porous metallic mesh by thermally desorbing and releasing a selected subset of contaminants from a contaminated mesh by rapidly raising the mesh to a pre-determined temperature step or plateau that has been chosen beforehand to preferentially desorb a particular chemical specie of interest, but not others. By providing a sufficiently long delay or dwell period in-between heating pulses, and by selecting the optimum plateau temperatures, then different contaminant species can be controllably released in well-defined batches at different times to a chemical detector in gaseous communication with the mesh. For some detectors, such as an Ion Mobility Spectrometer (IMS), separating different species in time before they enter the IMS allows the detector to have an enhanced selectivity.

  8. Temperature-programmed desorption studies of the interactions of OD and CO with Pt(111)

    NASA Astrophysics Data System (ADS)

    Weibel, Michael A.; Backstrand, Kyle M.; Curtiss, Thomas J.

    2000-01-01

    Temperature-programmed desorption (TPD) measurements were made to probe the interactions of hydroxyl radicals (OD) with Pt(111). A pure, intense molecular beam of OD was prepared by filtering the effluent from a supersonic corona discharge D2O/He source through an electrostatic hexapole. The hexapole selectively transmitted only OD radicals in the |J?M>=|{3}/{2} {3}/{2} {3}/{2}> rotational state and eliminated any D2O, oxygen or hydrogen atoms, or other contaminants from the beam. Experiments were carried out by dosing the surface with OD at a surface temperature of TS=275 K. Oxide states formed were characterized by desorption temperatures of TS=700, 735, and 790 K. The 735 K feature is believed to correspond to a near-surface oxide (PtOx) as seen previously in O3/Pt(111) studies. CO titration experiments revealed three CO2 desorption features: dominant features at TS=340 K and TS=440 K, the latter being perhaps due to oxidation via the PtOx. Another set of experiments were carried out by dosing OD at a surface temperature of TS=150 K. Major D2O desorption features were observed at TS=210 K corresponding to the decomposition of an OD-intermediate layer and at TS=170 K corresponding to molecular water desorption. The O2 TPD spectra showed the same three features observed at the higher dosing temperature, however, in substantially different ratios. CO oxidation experiments also revealed new behavior. Five CO2 desorption features were detected: the dominant features near TS?300 K and at TS?440 K, a smaller feature at TS=650 K, and two minor features at TS?185 and 230 K. Others have seen the latter two features previously in O2/CO Pt(111) studies.

  9. Monte Carlo simulations of temperature-programmed and isothermal desorption from single-crystal surfaces

    SciTech Connect

    Lombardo, S.J. . Dept. of Chemical Engineering Lawrence Berkeley Lab., CA )

    1990-08-01

    The kinetics of temperature-programmed and isothermal desorption have been simulated with a Monte Carlo model. Included in the model are the elementary steps of adsorption, surface diffusion, and desorption. Interactions between adsorbates and the metal as well as interactions between the adsorbates are taken into account with the Bond-Order-Conservation-Morse-Potential method. The shape, number, and location of the TPD peaks predicted by the simulations is shown to be sensitive to the binding energy, coverage, and coordination of the adsorbates. In addition, the occurrence of lateral interactions between adsorbates is seen to strongly effect the distribution of adsorbates is seen to strongly effect the distribution of adsorbates on the surface. Temperature-programmed desorption spectra of a single type of adsorbate have been simulated for the following adsorbate-metal systems: CO on Pd(100); H{sub 2} on Mo(100); and H{sub 2} on Ni(111). The model predictions are in good agreement with experimental observation. TPD spectra have also been simulated for two species coadsorbed on a surface; the model predictions are in qualitative agreement with the experimental results for H{sub 2} coadsorbed with strongly bound atomic species on Mo(100) and Fe(100) surfaces as well as for CO and H{sub 2} coadsorbed on Ni(100) and Rh(100) surfaces. Finally, the desorption kinetics of CO from Pd(100) and Ni(100) in the presence of gas-phase CO have been examined. The effect of pressure is seen to lead to an increase in the rate of desorption relative to the rate observed in the absence of gas-phase CO. This increase arises as a consequence of higher coverages and therefore stronger lateral interactions between the adsorbed CO molecules.

  10. TEMPERATURE-PROGRAMMED DESORPTION: PRINCIPLES, INSTRUMENT DESIGN, AND DEMONSTRATION WITH NAALH4

    SciTech Connect

    Stowe, A; Ragaiy Zidan, R

    2006-11-07

    This article is a brief introduction to temperature-programmed desorption (TPD), an analytical technique devised to analyze, in this case, materials for their potential as hydrogen storage materials. The principles and requirements of TPD are explained and the different components of a generic TPD apparatus are described. The construction of a modified TPD instrument from commercially available components is reported together with the control and acquisition technique used to create a TPD spectrum. The chemical and instrumental parameters to be considered in a typical TPD experiment and the analytical utility of the technique are demonstrated by the dehydrogenation of titanium-doped NaAlH{sub 4} by means of thermally programmed desorption.

  11. Temperature programmed desorption characterization of oxidized uranium surfaces: Relation to some gas-uranium reactions

    SciTech Connect

    Danon, A.; Koresh, J.E.; Mintz, M.H.

    1999-08-31

    The chemisorption characteristics and surface composition of oxidation overlayers developing on metals when exposed to oxidizing atmospheres are important in determining the protective ability of these layers against certain gas-phase reactions (e.g., corrosion and hydriding). In the present study, a special setup of supersonic molecular beam-temperature-programmed desorption was utilized to determine the different chemisorbed species present on oxidized uranium surfaces. The main identified species included water (in different binding forms) and hydrogen. The latter hydrogen originates from the water-uranium oxidation reaction, which produces uranium dioxide and two types of hydrogen: a near surface hydride and a surface-chemisorbed form that desorbs at a lower temperature than that of the hydride. Assignments of the different water desorption peaks to different binding sites were proposed. In general, four water desorption features were identified (labeled W{sub 0}, W{sub 1}, W{sub 2}, and W{sub 3}, respectively, in the order of increasing desorption temperatures). These features correspond to a reversibly chemisorbed molecular form (W{sub 0}), a more tightly bound water (chemisorbed on different type of oxide sites) or hydroxyl clusters (W{sub 1}), and strongly bounded (possibly isolated) hydroxyl groups (W{sub 2}). The highest temperature peak (W{sub 3}) is related to the formation of complex water-carbo-oxy compounds and is present only on oxidation overlayers, which contain proper chemisorbed carbo-oxy species. The relation of the water and hydrogen thermal release behavior to some problems addressed to certain effects observed in hydrogen-uranium and water-uranium reactions is discussed. For the latter, a microscopic mechanism is proposed.

  12. CO adsorption on Ce-Pt(111) studied with LEED, XPS, and temperature programmed desorption

    SciTech Connect

    Vermang, B.; Juel, M.; Raaen, S.

    2006-01-15

    CO adsorption on Ce-Pt(111) has been studied by temperature programmed desorption (TPD), low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS). Thin layers (1 to 3 ML) of Ce on Pt(111) form upon annealing to 1000 K a surface alloy which most likely is Pt terminated. The CO overlayer structure on Ce-Pt(111) at saturation coverage is argued to be an intermediate between (2x2) and c(4x2) superstructures. This intermediate structure exhibits a c(4x2) LEED pattern in which some of the spots appear together as ordered triangles. The thermal desorption spectra for the Ce-Pt(111) surface alloy are shifted down by a temperature of about 120 K compared to the CO desorption of pure Pt(111), most likely due to a change in the d-band due to hybridization between Ce and Pt states, which results in a weakening of the resonant interaction between CO 5{sigma} and Pt 5d states.

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

    NASA Astrophysics Data System (ADS)

    Rodrguez-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 thermal reaction is afforded. Since this work constitutes, to the best of our knowledge, the first effort to introduce multivariate analysis to TPD data, the procedures, algorithms and strategies employed are described in full detail.

  14. H(2)O Outgassing Properties of Fumed and Precipitated Silica Particles by Temperature-Programmed Desorption.

    PubMed

    Dinh; Balooch; LeMay

    2000-10-15

    Temperature-programmed desorption was performed at temperatures up to 850 K on as-received fumed and precipitated silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 38-61 kJ/mol. However, the activation energies of desorption for chemisorbed water varied from approximately 80 to >247 kJ/mol for fumed silica, Cab-O-Sil-M-7D, and approximately 96 to 155 kJ/mol for precipitated silica, Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>126 kJ/mol) will not escape silica surfaces in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (80-109 kJ/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies <126 kJ/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1-0.4 wt% of water in silica-reinforced polysiloxane formulations containing approximately 21% Cab-O-Sil-M-7D and approximately 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that the adsorbed H(2)O and the Si-OH bonds on the silica surfaces are the major contributors to water outgassing from these types of silica-filled polymers. Copyright 2000 Academic Press. PMID:11017751

  15. Interactions of N-alcohols with self-assembled monolayer surfaces on nickel(111) studied by temperature-programmed desorption

    NASA Astrophysics Data System (ADS)

    Vogt, Andrew Dale

    1999-12-01

    The interactions of molecules with self-assembled monolayer (SAM) surfaces formed on nickel (111) as studied by temperature-programmed desorption (TPD) are discussed. First, the adsorption of 11-mercaptoundecanoic acid (HS(CH 2)10COOH), 11-mercaptoundecanol (HS(CH2) 11OH) and octadecyl mercaptan (HS(CH2)17CH 3) was characterized by X-ray photoelectron spectroscopy (XPS) and angle-dependent XPS (ADXPS). These long-chain functionalized n-alkanethiols adsorbed onto a clean nickel (111) single crystal via their sulfur atom and the alkyl chain and the carboxyl-, hydroxyl- and methyl-terminal groups were disposed away from the nickel surface. The basic concepts of XPS, AMPS and TPD are discussed. Second, TPD showed that the interactions of low-molecular-weight straight-chain alcohols (n- CxH2x+1 OH for x = 1 through 6) with the carboxyl-, hydroxyl- and methyl-terminated SAM surfaces exhibited an alcohol-coverage-dependent effect on the alcohol's desorption energy based on their respective sets of TPD spectra at different alcohol coverages and based on the desorption spectra's subsequent analysis for desorption energy. The threshold TPD method (TTPD) was used to determine the desorption energy as a function of coverage for all alcohol-substrate pairs. For these adsorbate-substrate systems the desorption energies (TTPD) were the lowest (10--25 kJ mol-1) for the lowest relative alcohol coverages and increased to a desorption energy of 40--60 kJ mol-1 that was invariant with relative coverage after reaching a monolayer. The constant desorption energy (TTPD) at high relative coverages suggests there might be a completely formed hydrogen bonding network between adsorbates on the surfaces at alcohol coverages near a monolayer. The Redhead method, the "complete analysis" and the TTPD method are discussed and compared.

  16. Processes for desorption from LiAlO sub 2 treated with H sub 2 as studied by temperature programmed desorption

    SciTech Connect

    Fischer, A.K.

    1990-01-01

    The energetics and kinetics of the evolution of H{sub 2}O and H{sub 2} from LiAlO{sub 2} are being studied by the temperature programmed desorption technique. The concentrations of H{sub 2}, H{sub 2}O, N{sub 2}, and O{sub 2} in a helium stream during a temperature ramp are measured simultaneously with a mass spectrometer. Blank experiments with an empty sample tube showed that square wave spikes of H{sub 2} introduced into the helium gas stream were severely distorted by reaction with the tube walls. The tube could be stabilized, however, by sufficiently prolonged heat treatment with H{sub 2} so that H{sub 2} peaks would not be distorted up to approximately 923 K(650{degree}C). The amount of H{sub 2}adsorption/desorption is small compared to the amount of H{sub 2}O adsorption/desorption. After prolonged treatment with helium containing 990 ppm H{sub 2} at 400{degree}C, H{sub 2}O evolution into the He-H{sub 2} stream was observed during 473 to 1023 K (200 to 750{degree}C) ramps at rates of 2 or 5.6 K/min. The different peak shapes reflecting this process were deconvoluted to show that they are composites of only 2 or 3 reproducible processes. The activation energies and pre-exponential terms was evaluated. The different behavior originates in the differences among different surface sites for adsorption. The interpretation of higher temperature peaks (above 873 K (650{degree}C)) must still consider the possibility of contributions from interactions with steel walls. It was found that H{sub 2} enhances evolution of N{sub 2} from the steel. 1 tab., 6 figs., 11 refs.

  17. Temperature programed desorption of C{sub 2}H{sub 4} from pure and graphite-covered Pt(111)

    SciTech Connect

    Vermang, B.; Juel, M.; Raaen, S.

    2007-11-15

    Ethylene adsorption on Pt(111) at 95 K was studied by temperature programed desorption (TPD), low energy electron diffraction (LEED), and x-ray photoelectron spectroscopy. Ethylene desorbs reversibly at 112 K and irreversibly at 255 and 280 K. It is generally accepted that annealing of ethylene adsorbed on Pt(111) to 300 K results in a dehydrogenation to ethylidyne through an ethylidene intermediate. This was observed by a hydrogen desorption peak at 300 K. Also, hydrogenation of the adsorbed ethylene was observed by a small ethane desorption peak at 300 K. Upon heating to 700 K, the ethylidyne species will further dehydrogenate to carbidic carbon species with hydrogen desorption peaks at 460 and 640 K. If the carbidic species is heated to higher temperatures (up to 1000 K), it will further dehydrogenate and form graphitic islands which will accumulate by Ostwald ripening in larger islands at the step edges of the surface. After annealing the sample to 1000 K, a statistically distributed 8x8 superstructure of these graphite islands is achieved, as interpreted from A pattern in the LEED data. The TPD results indicate that ethylene adsorption on Pt(111) results in the formation of graphitic islands upon heating to 1000 K, contrary to previous conjectures of formation of a full graphite monolayer.

  18. New method for the temperature-programmed desorption (TPD) of ammonia experiment for characterization of zeolite acidity: a review.

    PubMed

    Niwa, Miki; Katada, Naonobu

    2013-10-01

    In this review, a method for the temperature-programmed desorption (TPD) of ammonia experiment for the characterization of zeolite acidity and its improvement by simultaneous IR measurement and DFT calculation are described. First, various methods of ammonia TPD are explained, since the measurements have been conducted under the concepts of kinetics, equilibrium, or diffusion control. It is however emphasized that the ubiquitous TPD experiment is governed by the equilibrium between ammonia molecules in the gas phase and on the surface. Therefore, a method to measure quantitatively the strength of the acid site (?H upon ammonia desorption) under equilibrium-controlled conditions is elucidated. Then, a quantitative relationship between ?H and H0 function is proposed, based on which the acid strength ?H can be converted into the H0 function. The identification of the desorption peaks and the quantitative measurement of the number of acid sites are then explained. In order to overcome a serious disadvantage of the method (i.e., no information is provided about the structure of acid sites), the simultaneous measurement of IR spectroscopy with ammonia TPD, named IRMS-TPD (infrared spectroscopy/mass spectrometry-temperature-programmed desorption), is proposed. Based on this improved measurement, Brnsted and Lewis acid sites were differentiated and the distribution of Brnsted OH was revealed. The acidity characterized by IRMS-TPD was further supported by the theoretical DFT calculation. Thus, the advanced study of zeolite acidity at the molecular level was made possible. Advantages and disadvantages of the ammonia TPD experiment are discussed, and understanding of the catalytic cracking activity based on the derived acidic profile is explained. PMID:23868494

  19. Dissociation energy for O2 release from gas-phase iron oxide clusters measured by temperature-programmed desorption experiments

    NASA Astrophysics Data System (ADS)

    Koyama, Kohei; Kudoh, Satoshi; Miyajima, Ken; Mafun, Fumitaka

    2015-04-01

    Thermal dissociation of gas phase iron oxide cluster ions, FenOm+ (n = 2-6), was observed by mass spectrometry. The dissociation processes were investigated by temperature-programmed desorption (TPD) measurements for different sized clusters. Oxygen molecules were found to be released from the cluster ions. The threshold energy required for dissociation, determined by analyzing TPD, was compared with the energies obtained by experiments of collision-induced dissociation and by calculations of density functional theory. The agreement of the energies indicates that the oxygen atoms bonded to the terminal site of clusters are more readily released into the gas phase than those in the bridge site.

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

    PubMed

    Pass-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. PMID:26018287

  1. Dosimeter-Type NOx Sensing Properties of KMnO4 and Its Electrical Conductivity during Temperature Programmed Desorption

    PubMed Central

    Groβ, Andrea; Kremling, Michael; Marr, Isabella; Kubinski, David J.; Visser, Jacobus H.; Tuller, Harry L.; Moos, Ralf

    2013-01-01

    An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release. PMID:23549366

  2. A technique for extending the precision and the range of temperature programmed desorption toward extremely low coverages

    NASA Astrophysics Data System (ADS)

    Haegel, Stefan; Zecho, Thomas; Wehner, Stefan

    2010-03-01

    In this paper, an improvement of the temperature programmed desorption (TPD) technique is introduced, which facilitates fully automated sampling of TPD spectra with excellent reproducibility, especially useful for extremely low coverages. By averaging many sampled TPD spectra, the range of the TPD technique can be extended toward lower coverages, as well as the quality of the spectra can be improved. This allows for easy extraction of information about the adsorbate-surface bond. A state of the art TPD apparatus with a two chamber setup and a high quality quadrupole mass spectrometer was extended by automated components. These are an automated gas dosing system, ensuring precise dosing of gas, combined with a motor driven sample manipulation unit and a liquid nitrogen cryostat with automatic refilling. In addition all components were controlled by a computer. A large number of TPD cycles could be sampled without the need of interaction of an operator. Here, it is shown for up to more than 400 TPD cycles. This opens a wide range of new interesting applications for the TPD technique, especially in the limit of zero coverage. Here, basic experiments on well known adsorbate systems are shown to view the ability and limit of this approach.

  3. Temperature-programmed desorption study of the selective oxidation of alcohols on silica-supported vanadium oxide.

    PubMed

    Feng, T; Vohs, J M

    2005-02-17

    The partial oxidation of methanol and ethanol on silica-supported vanadium oxide catalysts was studied using temperature-programmed desorption (TPD), Raman spectroscopy, and diffuse reflectance infrared spectroscopy (DRIFTS). Methanol TPD results for V2O5/SiO2 samples as a function of vanadia loading in conjunction with X-ray diffraction data and Raman spectra indicated that dispersed vanadia on silica agglomerates into vanadia crystallites during a CH3OH TPD experiment. For ethanol-dosed samples, agglomeration of the dispersed vanadia was less severe, and it was possible to measure the activation energy for the dehydrogenation of adsorbed ethoxides to produce CH3CHO. Assuming a preexponential factor of 10(13) s(-1), the activation energy for this reaction was estimated to be 132 kJ/mol. The results of this study further demonstrate that there is a relatively weak interaction between vanadia and silica and suggest that adsorbed methoxide species help facilitate agglomeration of dispersed vanadia. PMID:16851203

  4. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    SciTech Connect

    Tewell, Craig R.

    2002-08-19

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.

  5. Adsorption and decomposition of formic acid on MgO(001) surface as investigated by temperature programmed desorption and sum-frequency generation spectroscopy: Recurrence induced defect sites

    NASA Astrophysics Data System (ADS)

    Yamamoto, Hiroyoshi; Watanabe, Nobuyuki; Wada, Akihide; Domen, Kazunari; Hirose, Chiaki

    1997-03-01

    The change of the MgO(001) surface during the adsorption and thermal desorption of formic acid was investigated by temperature programmed desorption (TPD) and infrared-visible sum-frequency generation SFG spectroscopy. The TPD results revealed that the feature of desorption signals changed as the adsorption/thermal desorption process was repeated, despite no significant change of the low energy electron diffraction (LEED) pattern. The surface formate, produced by dissociative adsorption of formic acid, decomposed at 560 K and 700 K, giving H2O+CO and H2+CO2 as primary and minor products, respectively, but the broad desorption peak of H2O started to appear at 300 K. The 560 K peak appeared from an early stage, while the 700 K peak gained intensity as the experiment was repeated and the density of defects increased. The adsorption site for the 700 K peak was ascribed to the catalytic reaction of magnesia powder. The SFG spectra gave three resonance peaks of CH stretching bands at 2850 cm-1, 2870 cm-1, and 2920 cm-1 with a different dependence on the dose time, history of surface, and polarization of incident visible beam. The former two bands were assigned to the formates with bridged configuration, and the third band to the formate with unidentate configuration. The polarization dependence suggested that the CH bonds of bridged formates stood perpendicular to the surface, and that of the unidentate formate tilted approximately 30° from the surface normal. A vibration nonresonant background signal was present on the SFG signal, showing characteristic dependence on the polarization of incident light beams, as well as the coverage and history of the surface, and was interpreted as originating from the defect sites on the surface.

  6. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

    PubMed

    Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

    2016-05-15

    Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability. PMID:26939077

  7. Temperature-programmed decomposition desorption of mercury species over activated carbon sorbents for mercury removal from coal-derived fuel gas

    SciTech Connect

    M. Azhar Uddin; Masaki Ozaki; Eiji Sasaoka; Shengji Wu

    2009-09-15

    The mercury (Hg{sup 0}) removal process for coal-derived fuel gas in the integrated gasification combined cycle (IGCC) process will be one of the important issues for the development of a clean and highly efficient coal power generation system. Recently, iron-based sorbents, such as iron oxide (Fe{sub 2}O{sub 3}), supported iron oxides on TiO{sub 2}, and iron sulfides, were proposed as active mercury sorbents. The H{sub 2}S is one of the main impurity compounds in coal-derived fuel gas; therefore, H{sub 2}S injection is not necessary in this system. HCl is also another impurity in coal-derived fuel gas. In this study, the contribution of HCl to the mercury removal from coal-derived fuel gas by a commercial activated carbon (AC) was studied using a temperature-programmed decomposition desorption (TPDD) technique. The TPDD technique was applied to understand the decomposition characteristics of the mercury species on the sorbents. The Hg{sup 0}-removal experiments were carried out in a laboratory-scale fixed-bed reactor at 80-300{sup o}C using simulated fuel gas and a commercial AC, and the TPDD experiments were carried out in a U-tube reactor in an inert carrier gas (He or N{sub 2}) after mercury removal. The following results were obtained from this study: (1) HCl contributed to the mercury removal from the coal-derived fuel gas by the AC. (2) The mercury species captured on the AC in the HCl{sup -} and H{sub 2}S-presence system was more stable than that of the H{sub 2}S-presence system. (3) The stability of the mercury surface species formed on the AC in the H{sub 2}S-absence and HCl-presence system was similar to that of mercury chloride (HgClx) species. 25 refs., 12 figs., 1 tab.

  8. Characterization of olive oil volatiles by multi-step direct thermal desorption-comprehensive gas chromatography-time-of-flight mass spectrometry using a programmed temperature vaporizing injector.

    PubMed

    de Koning, Sjaak; Kaal, Erwin; Janssen, Hans-Gerd; van Platerink, Chris; Brinkman, Udo A Th

    2008-04-01

    The feasibility of a versatile system for multi-step direct thermal desorption (DTD) coupled to comprehensive gas chromatography (GC x GC) with time-of-flight mass spectrometric (TOF-MS) detection is studied. As an application the system is used for the characterization of fresh versus aged olive oil after treatment at 70, 175, 250 and 600 degrees C. PMID:17628576

  9. A study of the reactions of ethanol on CeO{sub 2} and Pd/CeO{sub 2} by steady state reactions, temperature programmed desorption, and in situ FT-IR

    SciTech Connect

    Yee, A.; Morrison, S.J.; Idriss, H.

    1999-09-10

    The reaction of ethanol on unreduced and H{sub 2}-reduced CeO{sub 2} and 1 wt% Pd/CeO{sub 2} has been investigated by steady state reactions, temperature programmed desorption (TPD), and in situ Fourier transform infrared (FT-IR) spectroscopy. Steady state reactions have shown a zero reaction order dependency for diatomic oxygen at and above 20%, while the addition of Pd to CeO{sub 2} decreases the apparent activation energy of the reaction from 75 kJ/mol on CeO{sub 2} alone to 40 kJ/mol (Pd/CeO{sub 2}). TPD experiments following ethanol adsorption on both CeO{sub 2} and Pd/CeO{sub 2} have shown desorption profiles corresponding to unreacted ethanol and various reaction and decomposition products (acetaldehyde, acetone, CO, CO{sub 2}, and methane). Ethanol conversion to reaction products was increased by the addition of Pd, from 15 to 30% on CeO{sub 2} and H{sub 2}-reduced CeO{sub 2}, to 71 and 63% on Pd/CeO{sub 2} and H{sub 2}-reduced Pd/CeO{sub 2}, respectively.

  10. Thermal Programmed Desorption of C32 H 66

    NASA Astrophysics Data System (ADS)

    Cisternas, M.; Del Campo, V.; Cabrera, A. L.; Volkmann, U. G.; Hansen, F. Y.; Taub, H.

    2011-03-01

    Alkanes are of interest as prototypes for more complex molecules and membranes. In this work we study the desorption kinetics of dotriacontane C32 adsorbed on Si O2 /Si substrate. We combine in our instrument High Resolution Ellipsometry (HRE) and Thermal Programmed Desorption (TPD). C32 monolayers were deposited in high vacuum from a Knudsen cell on the substrate, monitorizing sample thickness in situ with HRE. Film thickness was in the range of up to 100 AA, forming a parallel bilayer and perpendicular C32 layer. The Mass Spectrometer (RGA) of the TPD section was detecting the shift of the desorption peaks at different heating rates applied to the sample. The mass registered with the RGA was AMU 57 for parallel and perpendicular layers, due to the abundance of this mass value in the disintegration process of C32 in the mass spectrometers ionizer. Moreover, the AMU 57 signal does not interfere with other signals coming from residual gases in the vacuum chamber. The desorption energies obtained were ?Edes = 11,9 kJ/mol for the perpendicular bilayer and ?Edes = 23 ,5 kJ/mol for the parallel bilayer.

  11. Development of ultralow energy (110 eV) ion scattering spectrometry coupled with reflection absorption infrared spectroscopy and temperature programmed desorption for the investigation of molecular solids

    SciTech Connect

    Bag, Soumabha; Bhuin, Radha Gobinda; Methikkalam, Rabin Rajan J.; Pradeep, T.; Kephart, Luke; Walker, Jeff; Kuchta, Kevin; Martin, Dave; Wei, Jian

    2014-01-15

    Extremely surface specific information, limited to the first atomic layer of molecular surfaces, is essential to understand the chemistry and physics in upper atmospheric and interstellar environments. Ultra low energy ion scattering in the 110 eV window with mass selected ions can reveal extremely surface specific information which when coupled with reflection absorption infrared (RAIR) and temperature programmed desorption (TPD) spectroscopies, diverse chemical and physical properties of molecular species at surfaces could be derived. These experiments have to be performed at cryogenic temperatures and at ultra high vacuum conditions without the possibility of collisions of neutrals and background deposition in view of the poor ion intensities and consequent need for longer exposure times. Here we combine a highly optimized low energy ion optical system designed for such studies coupled with RAIR and TPD and its initial characterization. Despite the ultralow collision energies and long ion path lengths employed, the ion intensities at 1 eV have been significant to collect a scattered ion spectrum of 1000 counts/s for mass selected CH{sub 2}{sup +}.

  12. The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: a quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study.

    PubMed

    Graf, Barbara; Muhler, Martin

    2011-03-01

    The adsorption of carbon monoxide on an either unpromoted or potassium-promoted bulk iron catalyst was investigated at 303 K and 613 K by means of pulse chemisorption, adsorption calorimetry, temperature-programmed desorption and temperature-programmed surface reaction in hydrogen. CO was found to adsorb mainly molecularly in the absence of H(2) at 303 K, whereas the presence of H(2) induced CO dissociation at higher temperatures leading to the formation of CH(4) and H(2)O. The hydrogenation of atomic oxygen chemisorbed on metallic iron was found to occur faster than the hydrogenation of atomically adsorbed carbon. At 613 K CO adsorption occurred only dissociatively followed by recombinative CO(2) formation according to C(ads) + 2O(ads)→ CO(2(g)). The presence of the potassium promoter on the catalyst surface led to an increasing strength of the Fe-C bond both at 303 K and 613 K: the initial differential heat of molecular CO adsorption on the pure iron catalyst at 303 K amounted to 102 kJ mol(-1), whereas it increased to 110 kJ mol(-1) on the potassium-promoted sample, and the initial differential heat of dissociative CO adsorption on the unpromoted iron catalyst at 613 K amounted to 165 kJ mol(-1), which increased to 225 kJ mol(-1) in the presence of potassium. The calorimetric CO adsorption experiments also reveal a change of the energetic distribution of the CO adsorption sites present on the catalyst surface induced by the potassium promoter, which was found to block a fraction of the CO adsorption sites. PMID:21170422

  13. Water Vapor Adsorption - Desorption Behavior of a Small Piece of Desiccant Rotor in Temperature Swing

    NASA Astrophysics Data System (ADS)

    Washio, Yasuko; Kodama, Akio

    This study aims to clarify the adsorption / desorption behavior of water vapor onto / from a desiccant rotor in temperature swing. A magnetic suspension balance followed time variations of the weight of a small piece of desiccant rotor at various desorption temperature, adsorption / desorption time and their duration time ratio. Adsorption-desorption swing in steady state settled down at certain amplitude of the amount adsorbed keeping the balance of the adsorption and desorption rates averaged over each period. At low regeneration temperature around 40-50 oC, adsorption and desorption rates were affected considerably by the change of driving force of adsorption q*-q rather than the temperature dependence of the mass transfer coefficient. At constant adsorption and desorption air conditions, the adsorption /desorption rates could be summarized by the amount of adsorption and temperature, independently of the length of cycle time. Also, region of the amount of adsorption at which adsorption - desorption swing occurred was predicted considering the adsorption / desorption rates - amount adsorbed relationship and the adsorption / desorption duration ratio.

  14. Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory

    PubMed Central

    2014-01-01

    Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt3Zr(0001) substrate by oxidation in 1 × 10–7 mbar of O2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O–Zr–O) films on the alloy; only a small area fraction (10–15%) is covered by ZrO2 clusters (thickness ∼0.5–10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt3Zr substrate by ZrO2, that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO2 films are between those of metallic Zr and thick (bulklike) ZrO2. Therefore, the assignment of such XPS core level shifts to substoichiometric ZrOx is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO2 films or metal/ZrO2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators. PMID:25688293

  15. Acoustic Desorption from a Room Temperature Ionic Liquid.

    NASA Astrophysics Data System (ADS)

    Harris, Peter; Tracy, Eugene; Cooke, William

    2007-11-01

    We report on the acoustic desorption of ions from the surface of a room temperature ionic liquid (RTIL) under vacuum. Our RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate, remains a stable liquid at extremely low pressures (<10-9 torr). Using the 2^nd harmonic of a Nd:YAG laser, 2ns pulse time, we ablate the backside of a metal foil, generating an acoustic pulse that propagates through the foil, desorbing ions off the surface of the RTIL. We determine the m/q of desorbed ions via time of flight (TOF) measurements from an imaging micro-channel plate detector. We detect both positive and negative ion species, depending on the extraction and acceleration voltages. Our TOF spectra demonstrate our acoustic pulses are of short duration (<20ns), generating mass spectra with good temporal resolution (<40ns FWHM @ t=9000ns), that are stable and reproducible. We discuss the variation of desorbed ion yield as a function of acoustic pulse strength, metal foil properties and extraction fields.

  16. Probing the interaction of hydrogen chloride with low-temperature water ice surfaces using thermal and electron-stimulated desorption.

    PubMed

    Olanrewaju, Babajide O; Herring-Captain, Janine; Grieves, Gregory A; Aleksandrov, Alex; Orlando, Thomas M

    2011-06-16

    The interaction and autoionization of HCl on low-temperature (80-140 K) water ice surfaces has been studied using low-energy (5-250 eV) electron-stimulated desorption (ESD) and temperature programmed desorption (TPD). There is a reduction of H(+) and H(2)(+) and a concomitant increase in H(+)(H(2)O)(n=1-7) ESD yields due to the presence of submonolayer quantities of HCl. These changes are consistent with HCl induced reduction of dangling bonds required for H(+) and H(2)(+) ESD and increased hole localization necessary for H(+)(H(2)O)(n=1-7) ESD. For low coverages, this can involve nonactivated autoionization of HCl, even at temperatures as low as 80 K; well below those typical of polar stratospheric cloud particles. The uptake and autoionization of HCl is supported by TPD studies which show that for HCl doses ?0.5 0.2 ML (ML = monolayer) at 110 K, desorption of HCl begins at 115 K and peaks at 180 K. The former is associated with adsorption of a small amount of molecular HCl and is strongly dependent on the annealing history of the ice. The latter peak at 180 K is commensurate with desorption of HCl via recombinative desorption of solvated separated ion pairs. The activation energy for second-order desorption of HCl initially in the ionized state is 43 2 kJ/mol. This is close to the zero-order activation energy for ice desorption. PMID:21548613

  17. Room-temperature associative adsorption and thermal dissociative desorption of trifluorobenzene on Si(100)2x1

    NASA Astrophysics Data System (ADS)

    Zhou, Xiaojing; Leung, K. T.

    2004-03-01

    Functionalization of Si(100) has been extensively investigated in ultra-high vacuum and in solutions for its potential applications in molecular devices and chemical sensors. Aromatic molecules are good candidates because of their rich chemical properties, low cost and widespread use in industry. In the present work, trifluorobenzene (TFB) is used to study the effects of halogen substitution on benchmark molecules such as benzene and ethylene. Unlike halogenated ethylenes that exhibit dissociative adsorption at room temperature (RT), TFB is found to adsorb on Si(100) 2x1 associatively at RT and to undergo partial dissociation at a higher substrate temperature. Molecular desorption states at 380 K, 430K and 520K have also been observed in our temperature programmed desorption experiment, which is consistent with the desorption patterns of benzene and toluene. Additional desorption species of C6H6, SiF2 and F2 occurring over the same temperature range indicate a thermally driven dissociation process. Furthermore, ab initio calculation (with full geometry optimization) shows that selective adsorption occurs at the 2,5 position of the ring , which may be used for patterning of molecular devices on Si(100).

  18. Threshold character of temperatures on deuterium desorption from the Mg-Zr composite

    NASA Astrophysics Data System (ADS)

    Neklyudov, I. M.; Morozov, O. M.; Kulish, V. G.; Zhurba, V. I.; Lomino, N. S.; Ovcharenko, V. D.; Kuprin, O. S.

    2011-06-01

    The plasma evaporation-sputtering method was used to manufacture composite materials of the Mg-Zr system. The ion-implanted deuterium desorption temperature variations depending on the component concentrations were studied. It has been established that the introduction of a Zr impurity to magnesium leads to the significant decrease of the deuterium desorption temperature (~400K) as compared to the release from Mg samples. A step-like form of the curve of the deuterium desorption temperature testifies to presence of two various structural conditions at composite Mg-Zr depending on the relation of components. The hydrogen desorption data obtained using Mg-Zr composites can be used for the further invrstigations into the hydrogen storage materials containing chemical elements with a low solubility in the alloy components.

  19. Reversibility, Dopant Desorption, and Tunneling in the Temperature-Dependent Conductivity of Type-Separated, Conductive Carbon Nanotube Networks

    SciTech Connect

    Barnes, T. M.; Blackburn, J. L.; van de Lagemaat, J.; Coutts, T. J.; Heben, M. J.

    2008-09-01

    We present a comprehensive study of the effects of doping and temperature on the conductivity of single-walled carbon nanotube (SWNT) networks. We investigated nearly type-pure networks as well as networks comprising precisely tuned mixtures of metallic and semiconducting tubes. Networks were studied in their as-produced state and after treatments with nitric acid, thionyl chloride, and hydrazine to explore the effects of both intentional and adventitious doping. For intentionally and adventitiously doped networks, the sheet resistance (R{sub s}) exhibits an irreversible increase with temperature above {approx}350 K. Dopant desorption is shown to be the main cause of this increase and the observed hysteresis in the temperature-dependent resistivity. Both thermal and chemical dedoping produced networks free of hysteresis. Temperature-programmed desorption data showed that dopants are most strongly bound to the metallic tubes and that networks consisting of metallic tubes exhibit the best thermal stability. At temperatures below the dopant desorption threshold, conductivity in the networks is primarily controlled by thermally assisted tunneling through barriers at the intertube or interbundle junctions.

  20. Low-Temperature, Vacuum-Aided Thermal Desorption Studies on a Simulated Organic Sludge Waste

    SciTech Connect

    R. K. Farnsworth; D. R. Peterman; Gary L. Anderson; T. G. Garn

    2002-12-01

    This report describes an initial set of small scale lab tests conducted on surrogate waste materials to investigate mass release behavior of volatile organics (VOCs) from a solidified liquid organic sludge matrix under vacuumaided, low-temperature thermal desorption conditions. Low temperature thermal desorption is being considered as a potential processing technology alternative to incineration, to remove gas generation limitations affecting the transportation of transuranic (TRU) contaminated organic sludge wastes to a designated off-site repository (i.e., the Waste Isolation Pilot Plant). The lab-scale tests provide initial exploratory level information on temperature profiles and rates of volatile organic desorption for a range of initial VOC/oil liquid mixture concentrations in a calcium silicate matrix, under low temperature heating and vacuum boundary conditions that are representative of potentially desirable in-drum desorption conditions. The results of these tests indicate that reduced operating pressures have a potential for significantly enhancing the rate of thermal desorption experienced from a liquid organic/oil solidified sludge waste. Furthermore, the results indicate that in-drum thermal desorption can be performed on organic sludge wastes, at reduced pressures, while maintaining an operating temperature sufficiently low to prevent destruction of the waste drum packaging materials (confinement) surrounding the waste. The results also indicate that VOC release behavior/rates in the vacuum thermal desorption process cannot be represented by a simple liquid-liquid mass-diffusion model, since overall mass release rates observed are generally two orders of magnitude greater than predicted by simple liquid-liquid mass diffusion. This is partially attributed to the effects of the transient temperature profiles within the sludge during heat up; however, the primary cause is thought to be micro boiling of the volatile organics within the simulated sludge. Micro boiling of VOCs would be expected to occur in localized volumes within the organic sludge where temperatures exceed the volatile organic saturation temperature sufficiently to form vapor bubbles. Further model based evaluations reflecting the transient temperatures, local boiling, and subsequent vapor in liquid/sludge transport conditions are needed, with supporting controlled testing of the vacuum-aided thermal desorption process at small and full-scale conditions in order to fully develop this process.

  1. Effect of temperature and particle size on the thermal desorption of PCBs from contaminated soil.

    PubMed

    Qi, Zhifu; Chen, Tong; Bai, Sihong; Yan, Mi; Lu, Shengyong; Buekens, Alfons; Yan, Jianhua; Bulm?u, Cora; Li, Xiaodong

    2014-03-01

    Thermal desorption is widely used for remediation of soil contaminated with volatiles, such as solvents and distillates. In this study, a soil contaminated with semivolatile polychlorinated biphenyls (PCBs) was sampled at an interim storage point for waste PCB transformers and heated to temperatures from 300 to 600 C in a flow of nitrogen to investigate the effect of temperature and particle size on thermal desorption. Two size fractions were tested: coarse soil of 420-841 ?m and fine soil with particles <250 ?m. A PCB removal efficiency of 98.0 % was attained after 1 h of thermal treatment at 600 C. The residual amount of PCBs in this soil decreased with rising thermal treatment temperature while the amount transferred to the gas phase increased up to 550 C; at 600 C, destruction of PCBs became more obvious. At low temperature, the thermally treated soil still had a similar PCB homologue distribution as raw soil, indicating thermal desorption as a main mechanism in removal. Dechlorination and decomposition increasingly occurred at high temperature, since shifts in average chlorination level were observed, from 3.34 in the raw soil to 2.75 in soil treated at 600 C. Fine soil particles showed higher removal efficiency and destruction efficiency than coarse particles, suggesting that desorption from coarse particles is influenced by mass transfer. PMID:24352542

  2. CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R822721C697)

    EPA Science Inventory

    This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4mm ID quartz bed enclosed in an electric furnace. ...

  3. CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R826694C697)

    EPA Science Inventory

    This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4mm ID quartz bed enclosed in an electric furnace. ...

  4. CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R822721C697)

    EPA Science Inventory

    This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

  5. CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R826694C697)

    EPA Science Inventory

    This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

  6. EFFECTS OF TEMPERATURE ON TRICHLOROETHYLENE DESORPTION FROM SILICA GEL AND NATURAL SEDIMENTS. 2. KINETICS. (R822626)

    EPA Science Inventory

    Isothermal desorption rates were measured at 15, 30, and 60 src="/ncer/pubs/images/deg.gif">C for trichloroethylene (TCE) on a silica gel,
    an aquifer sediment, a soil, a sand fraction, and a clay and silt fraction, all
    at 100% relative humidity. Temperature-st...

  7. Acoustic Desorption from a Room Temperature Ionic Liquid.

    NASA Astrophysics Data System (ADS)

    Harris, Peter; Tracy, Eugene; Cooke, William

    2007-06-01

    We use laser induced acoustic pulses to efficiently desorb ions from a Room Temperature Ionic Liquid (RTIL) in vacuum. Our RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate, remains a stable liquid at pressures exceeding 10-9 torr. We use the 2^nd harmonic of a Nd:YAG laser, 2ns pulse time, to generate acoustic pulses via laser ablation of the backside of a metal foil. Both negative and positive ions are desorbed from the liquid RTIL surface on the front side of the foil. The m/q of ejected ions is detected via TOF measurements from an imaging micro-channel plate detector. We measure the time our acoustic pulse reaches the RTIL surface by detecting the ejected electron signal. We present data showing the variation of desorbed ion yield as a function of the amplitude and shape of the incident acoustic pulse.

  8. Investigation of the interaction of benzene with vanadium-molybdenum oxide catalysts by programmed thermal desorption

    SciTech Connect

    Belokopytov, Yu.V.; Pyatnitskii, Yu.I.; Grebennikov, Yu.N.

    1985-09-01

    Programmed thermal desorption was used to investigate the interaction of benzene with vanadium-molybdenum oxide catalysts. It was established that the amount of maleic anhydride desorbed from the catalyst surface depends on the catalyst composition and that it varies with its activity and selectivity.

  9. Low-temperature thermal desorption of diesel polluted soil: influence of temperature and soil texture on contaminant removal kinetics.

    PubMed

    Falciglia, P P; Giustra, M G; Vagliasindi, F G A

    2011-01-15

    Five soil size aggregate fractions, corresponding to coarse (500-840 ?m), medium (200-350 ?m), fine (75-200 ?m) sand, silt (10-75 ?m) and clay (<4 ?m), were artificially contaminated with diesel, and thermally treated using a laboratory scale apparatus to investigate the effect of soil texture on contaminant adsorption and removal. Ex situ thermal process was simulated using helium as the carrier gas at a flow rate of 1.5 L min(-1), different temperatures (100-300 C) and different treatment times (5-30 min). The amount of contaminant adsorbed on the soil and the residual amount after thermal treatment was determined by gas chromatography. Results showed that adsorption phenomena and desorption efficiency were affected by the soil texture and that temperature and time of treatment were key factors in remedial process. A temperature of 175 C is sufficient to remedy diesel polluted sandy and silty soils, whereas a higher temperature (250 C) is needed for clays. Thermal desorption of diesel polluted soil was shown to be governed by first-order kinetics. Results are of practical interest and may be used in scaling-up and designing desorption systems for preliminary cost and optimal condition assessment. PMID:20940088

  10. Variable Temperature Infrared Spectroscopy Investigations of Benzoic Acid Desorption from Sodium and Calcium Montmorillonite Clays.

    PubMed

    Nickels, Tara M; Ingram, Audrey L; Maraoulaite, Dalia K; White, Robert L

    2015-12-01

    Processes involved in thermal desorption of benzoic acid from sodium and calcium montmorillonite clays are investigated by using variable temperature diffuse reflection Fourier transform infrared spectroscopy (DRIFTS). By monitoring the temperature dependence of infrared absorbance bands while heating samples, subtle changes in molecular vibrations are detected and employed to characterize specific benzoic acid adsorption sites. Abrupt changes in benzoic acid adsorption site properties occur for both clay samples at about 125 C. Difference spectra absorbance band frequency variations indicate that adsorbed benzoic acid interacts with interlayer cations through water bridges and that these interactions can be disrupted by the presence of organic anions, in particular, benzoate. PMID:26647147

  11. Adsorption, diffusion, dewetting, and entrapment of acetone on Ni(111), surface-modified silicon, and amorphous solid water studied by time-of-flight secondary ion mass spectrometry and temperature programmed desorption

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2011-10-01

    Interactions of acetone with the silicon surfaces terminated with hydrogen, hydroxyl, and perfluorocarbon are investigated; results are compared to those on amorphous solid water (ASW) to gain insights into the roles of hydrogen bonds in surface diffusion and hydration of acetone adspecies. The surface mobility of acetone occurs at 60 K irrespective of the surface functional groups. Cooperative diffusion of adspecies results in a 2D liquid phase on the H- and perfluorocarbon-terminated surfaces, whereas cooperativity tends to be quenched via hydrogen bonding on the OH-terminated surface, thereby forming residues that diffuse slowly on the surface after evaporation of the physisorbed species (i.e., 2D liquid). The interaction of acetone adspecies on the non-porous ASW surface resembles that on the OH-terminated Si surface, but the acetone molecules tend to be hydrated on the porous ASW film, as evidenced by their desorption during the glass-liquid transition and crystallization of water. The roles of micropores in hydration of acetone molecules are discussed from comparison with the results using mesoporous Si substrates.

  12. Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

    SciTech Connect

    Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina; Yong-Hyun, Kim

    2013-01-01

    It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principles total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.

  13. Threshold character of temperatures on deuterium thermal desorption in Mg-V composite grown atom-by-atom

    NASA Astrophysics Data System (ADS)

    Neklyudov, I. M.; Morozov, O. M.; Kulish, V. G.; Zhurba, V. I.; Galitskiy, A. G.; Lomino, N. S.; Kuprin, A. S.; Ovcharenko, V. D.; Reshetnyak, E. N.

    2012-08-01

    The plasma evaporation-sputtering method was applied to make composite materials of the Mg-V system. The ion-implanted deuterium desorption temperature variations as a function of the component concentration were studied. It has been established that, by introducing vanadium into magnesium, the deuterium desorption temperature can be appreciably decreased (to 300-330 K) in comparison with the case of deuterium desorption from magnesium (~800 K). A step-like form of the curve of deuterium desorption temperature evidences on the presence of two different structure states of the Mg-V system depending on the ratio of components. The deuterium temperature decrease can be caused by filamentary inclusions formed, in the process of composite making and annealing, by the insoluble component (vanadium) atoms providing the deuterium diffusion from the sample at a lower temperature (channels for deuterium diffusion through the surface barrier). A necessary high diffusion mobility of deuterium is provided by the amorphous state of Mg83+xVx samples. The deuterium desorption data obtained on the example of Mg-V and Mg-Zr composites provide support for further research into hydrogen storage materials containing low-soluble chemical elements in the alloy components.

  14. Kinetics of desorption of KCL from polyvinyl alcohol-borate hydrogel in aqueous-alcoholic solvents at different temperatures

    NASA Astrophysics Data System (ADS)

    Saeed, Rehana; Abdeen, Zain Ul

    2015-11-01

    Desorption kinetics of adsorbed KCl from Polyvinyl alcohol borate hydrogel was studied by conductivity method in aqueous system and aqueous binary solvent system using 50% aqueous-methanol, aqueous- ethanol and aqueous-propanol at different temperature ranging from 293 to 313 K. Desorption process follows pseudo first order and intra particle diffusion kinetics was analyzed on the basis of linear regression coefficient R 2 and chi square test χ2 values. The process of desorption of KCl from hydrogel was favorable in aqueous system, the study reveals the fact that the polarity of solvent influenced the kinetics of desorption, on decrement of polarity of solvent rate, rate constant and intra particle rate constant decreases. Based on intra particle kinetic equation fitting it was concluded that desorption was initiated by removal of ions from surface of hydrogel later on ions interacted inside the cross linked unit was also become free. Temperature enhances the rate, rate constant and intra particle rate constant. Thermodynamic parameters attributed towards the fact that the process of desorption of KCl from hydrogel is non-spontaneous in nature.

  15. Effect of temperature on the desorption and decomposition of mustard from activated carbon

    SciTech Connect

    Karwacki, C.J.; Buchanan, J.H.; Mahle, J.J.; Buettner, L.C.; Wagner, G.W.

    1999-12-07

    Experimental data are reported for the desorption of bis-2-chloroethyl sulfide, (a sulfur mustard or HD) and its decomposition products from activated coconut shell carbon (CSC). The results show that under equilibrium conditions changes in the HD partial pressure are affected primarily by its loading and temperature of the adsorbent. The partial pressure of adsorbed HD is found to increase by about a decade for each 25 C increase in temperature for CSC containing 0.01--0.1 g/g HD. Adsorption equilibria of HD appear to be little affected by coadsorbed water. Although complicated by its decomposition, the distribution of adsorbed HD (of known amount) appears to occupy pores of similar energy whether dry or in the presence of adsorbed water. On dry CSC adsorbed HD appears stable, while in the presence of water its decomposition is marked by hydrolysis at low temperature and thermal decomposition at elevated temperatures. The principal volatile products desorbed are 1,4-thioxane, 2-chloroethyl vinyl sulfide and 1,4-dithiane, with the latter favoring elevated temperatures.

  16. Thermal desorption of ammonia from crystalline forsterite surfaces

    NASA Astrophysics Data System (ADS)

    Suhasaria, T.; Thrower, J. D.; Zacharias, H.

    2015-12-01

    The thermal desorption of ammonia (NH3) from single crystal forsterite (010) has been investigated using temperature-programmed desorption. The effect of defects on the desorption process has been probed by the use of a rough cut forsterite surface prepared from the cleaved forsterite sample. Several approaches have been used to extract the desorption energy and pre-exponential factor describing the desorption kinetics. In the sub-monolayer coverage regime, the NH3 desorption shows a broad distribution of desorption energies, indicating the presence of different adsorption sites, which results in an apparent coverage-dependent desorption energy. This distribution is sensitive to the surface roughness with the cut forsterite surface displaying a significantly broader distribution of desorption energies compared to the cleaved forsterite surface. The cut forsterite surface exhibits sites with desorption energies up to 62.5 kJ mol-1 in comparison to a desorption energy of up to 58.0 kJ mol-1 for the cleaved surface. Multilayer desorption is independent of the nature of the forsterite surface used, with a desorption energy of (25.8 0.9) kJ mol-1. On astrophysically relevant heating time-scales, the presence of a coverage-dependent desorption energy distribution results in a lengthening of the NH3 desorption time-scale by 5.9 104 yr compared to that expected for a single desorption energy. In addition, the presence of a larger number of high-energy adsorption sites on the rougher cut forsterite surface leads to a further lengthening of ca. 7000 yr.

  17. Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

    SciTech Connect

    Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

    2014-09-18

    The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

  18. EFFECTS OF TEMPERATURE ON TRICHLOROETHYLENE DESORPTION FROM SILICA GEL AND NATURAL SEDIMENTS. 1. ISOTHERMS. (R822626)

    EPA Science Inventory

    Aqueous phase isotherms were calculated from vapor phase desorption isotherms
    measured at 15, 30, and 60 C for
    trichloroethylene on a silica gel, an aquifer sediment, a soil, a sand fraction,
    and a clay and silt fraction, all at...

  19. Desorption of InSb(001) native oxide and surface smoothing induced by low temperature annealing under molecular hydrogen flow

    NASA Astrophysics Data System (ADS)

    Tessler, R.; Saguy, C.; Klin, O.; Greenberg, S.; Weiss, E.; Akhvlediani, R.; Edrei, R.; Hoffman, A.

    2007-01-01

    The preparation of InSb (001) oxygen-free surfaces by thermal annealing at relatively low temperatures under molecular hydrogen flow is reported. This process is compared with thermal oxide desorption (TOD) at 400C under ultrahigh vacuum conditions. Molecular hydrogen cleaning (MHC) at substrate temperature of 250C and at hydrogen pressure of 510-6Torr resulted in complete desorption of the native oxide layer. Furthermore, no carbon contamination was observed on the surface following this treatment. The surface morphology of the samples following this process was found to be very smooth without any droplet structure. The In:Sb surface stoichiometry was nearly 1:1 along the MHC process. In addition, annealing the sample at 400C in vacuum after oxide removal by MHC maintains the smoothness and the stoichiometry of the surface. In contrast, TOD at 400C of an oxidized InSb surface in vacuum does not result in complete oxide removal from the surface. Furthermore, small droplets associated with In are produced at this annealing temperature. The surface stoichiometry shows In enrichment after TOD in vacuum above 360C. The surface composition and chemical bonding were monitored by Auger electron spectroscopy and x-ray photoelectron spectroscopy as a function of process parameters. The surface morphology was analyzed by atomic force microscopy.

  20. Temperature and concentration effects in electron-stimulated desorption of sodium atoms from sodium layers adsorbed on tungsten coated with a gold film

    NASA Astrophysics Data System (ADS)

    Ageev, V. N.; Kuznetsov, Yu. A.; Potekhina, N. D.

    2008-08-01

    The yield and energy distributions of sodium atoms upon electron-stimulated desorption from sodium layers adsorbed on tungsten coated with a gold film are investigated for the first time as functions of the thickness of the gold film, the concentration of deposited sodium, and the surface temperature. It is found that the energy distributions exhibit two peaks, namely, a narrow peak with a maximum at about 0.15 eV, whose intensity continuously increases with increasing temperature, and a broad peak with a maximum at about 0.35 eV, whose intensity either decreases or remains constant with increasing temperature. It is shown that both peaks arise as a result of the same excitation, which gives rise to different channels of electron-stimulated desorption of sodium atoms. Possible mechanisms of electron-stimulated desorption and the kinetics of destruction of the surface coating are discussed.

  1. Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces.

    PubMed

    Smith, R Scott; May, R Alan; Kay, Bruce D

    2016-03-01

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from graphene-covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature-programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multilayer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The nonalignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates. PMID:26595145

  2. Chemometric optimization of a low-temperature plasma source design for ambient desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Albert, Anastasia; Engelhard, Carsten

    2015-03-01

    Low-temperature plasmas (LTPs) are attractive sources for atomic and molecular mass spectrometry (MS). In the past, the LTP probe, which was first described by Harper et al., was used successfully for direct molecular mass spectrometric analysis with minimal sample pretreatment in a variety of applications. Unfortunately, the desorption/ionization source itself is commercially not available and custom-built LTP set-ups with varying geometry and operational configurations were utilized in the past. In the present study, a rapid chemometrics approach based on systematic experiments and multivariate data analysis was used to optimize the LTP probe geometry and positioning relative to the atmospheric-pressure inlet of a mass spectrometer. Several parameters were studied including the probe geometry, electrode configuration, quartz tube dimensions, probe positioning and operating conditions. It was found that the plasma-to-MS-inlet distance, the plasma-to-sample-plate distance, and the angle between the latter are very important. Additional effects on the analytical performance were found for the outer electrode width, the positioning of the electrodes, the inner diameter of the quartz tube, the quartz wall thickness, and the gas flow. All experiments were performed using additional heating of the sample to enhance thermal desorption and maximize the signal (T = 150 C). After software-assisted optimization, attractive detection limits were achieved (e.g., 1.8 10- 7 mol/L for 4-acetamidothiophenol). Moreover, relative standard deviation (RSD) improved from values of up to 30% before optimization to < 15% RSD after the procedure was completed. This chemometrics approach for method optimization is not limited to LTP-MS and considered to be attractive for other plasma-based instrumentation as well.

  3. Desorption kinetics from a surface derived from direct imaging of the adsorbate layer

    NASA Astrophysics Data System (ADS)

    Gnther, S.; Mente?, T. O.; Nio, M. A.; Locatelli, A.; Bcklein, S.; Wintterlin, J.

    2014-05-01

    There are numerous indications that adsorbed particles on a surface do not desorb statistically, but that their spatial distribution is important. Evidence almost exclusively comes from temperature-programmed desorption, the standard method for measuring desorption rates. However, this method, as a kinetics experiment, cannot uniquely prove an atomic mechanism. Here we report a low-energy electron microscopy investigation in which a surface is microscopically imaged while simultaneously temperature-programmed desorption is recorded. The data show that during desorption of oxygen molecules from a silver single crystal surface, islands of oxygen atoms are present. By correlating the microscopy and the kinetics data, a model is derived that includes the shapes of the islands and assumes that the oxygen molecules desorb from the island edges. The model quantitatively reproduces the complex desorption kinetics, confirming that desorption is affected by islands and that the often used mean-field treatment is inappropriate.

  4. Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

    SciTech Connect

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2014-05-08

    We find that NO dosed on rutile TiO2(110)-11 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 2 sec at an NO flux of 1.2 1014 NO/cm2?sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VOs) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, the N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VOs passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.

  5. N2 and CO Desorption Energies from Water Ice

    NASA Astrophysics Data System (ADS)

    Fayolle, Edith C.; Balfe, Jodi; Loomis, Ryan; Bergner, Jennifer; Graninger, Dawn; Rajappan, Mahesh; Öberg, Karin I.

    2016-01-01

    The relative desorption energies of CO and N2 are key to interpretations of observed interstellar CO and N2 abundance patterns, including the well-documented CO and N2H+ anti-correlations in disks, protostars, and molecular cloud cores. Based on laboratory experiments on pure CO and N2 ice desorption, the difference between CO and N2 desorption energies is small; the N2-to-CO desorption energy ratio is 0.93 ± 0.03. Interstellar ices are not pure, however, and in this study we explore the effect of water ice on the desorption energy ratio of the two molecules. We present temperature programmed desorption experiments of different coverages of 13CO and 15N2 on porous and compact amorphous water ices and, for reference, of pure ices. In all experiments, 15N2 desorption begins a few degrees before the onset of 13CO desorption. The 15N2 and 13CO energy barriers are 770 and 866 K for the pure ices, 1034-1143 K and 1155-1298 K for different submonolayer coverages on compact water ice, and 1435 and 1575 K for ˜1 ML of ice on top of porous water ice. For all equivalent experiments, the N2-to-CO desorption energy ratio is consistently 0.9. Whenever CO and N2 ice reside in similar ice environments (e.g., experience a similar degree of interaction with water ice) their desorption temperatures should thus be within a few degrees of one another. A smaller N2-to-CO desorption energy ratio may be present in interstellar and circumstellar environments if the average CO ice molecules interacts more with water ice compared to the average N2 molecules.

  6. Thermal desorption of CO from Mo(110)

    NASA Astrophysics Data System (ADS)

    Raaen, S.; Juel, M.

    2003-03-01

    Adsorption of CO on Mo(110) has been studied by temperature programmed desorption (TPD), photoelectron spectroscopy, and Monte-Carlo simulations. Carbon monoxide is partly dissociated when adsorbed on this surface at ambient temperatures. Two desorption regions, 250-400 K (molecular adsorption) and 850-1100 K (dissociative adsorption) are observed in the TPD spectra. Molecular species were identified by orbitals present in the photoemission measurements. It was found that the desorption signal corresponding to dissociative adsorption saturates rapidly for CO exposures below 1L, whereas the desorption intensity corresponding to molecular adsorption increases with exposure up to about 5L. Interpretation of desorption data is generally not straight forward due to the dependence of several properties of the surface and absorbed species. Therefore, the experimental data for the molecular adsorption region has been compared to Monte-Carlo simulations. The algorithm proposed by Meng and Weinberg [1] was employed. The presence of dissociated species on the surface has been modeled. Two different adsorption sites, "on-top" and "bridge" sites, was considered. Three different near neighbor interactions on the bcc(110) surface have been included. [1] B.Meng and W.H. Weinberg, J. Chem. Phys. 100, 5280 (1994).

  7. Temperature-dependent phase transition and desorption free energy of sodium dodecyl sulfate at the water/vapor interface: approaches from molecular dynamics simulations.

    PubMed

    Chen, Meng; Lu, Xiancai; Liu, Xiandong; Hou, Qingfeng; Zhu, Youyi; Zhou, Huiqun

    2014-09-01

    Adsorption of surfactants at the water/vapor interface depends upon their chemical potential at the interface, which is generally temperature-dependent. Molecular dynamics simulations have been performed to reveal temperature influences on the microstructure of sodium dodecyl sulfate (SDS) molecule adsorption layer. At room temperature, SDS molecules aggregate at the interface, being in a liquid-expanded phase, whereas they tend to spread out and probably transit to a gaseous phase as the temperature increases to above 318 K. This phase transition has been confirmed by the temperature-dependent changes in two-dimensional array, tilt angles, and immersion depths to the aqueous phase of SDS molecules. The aggregation of SDS molecules accompanies with larger immersion depths, more coordination of Na(+) ions, and less coordination of water. Desorption free energy profiles show that higher desorption free energy appears for SDS molecules at the aggregate state at low temperatures, but no energy barrier is observed. The shapes of desorption free energy profiles depend upon the distribution of SDS at the interface, which, in turn, is related to the phase state of SDS. Our study sheds light on the development of adsorption thermodynamics and kinetics theories. PMID:25127193

  8. Desorption of Hg(II) and Sb(V) on extracellular polymeric substances: effects of pH, EDTA, Ca(II) and temperature shocks.

    PubMed

    Zhang, Daoyong; Lee, Duu-Jong; Pan, Xiangliang

    2013-01-01

    Extracellular polymeric substances (EPS) existed ubiquitously in biological systems affect the mobility and availability of heavy metals in the environments. The adsorption-desorption behaviors of Hg(II) and Sb(V) on EPS were investigated. The sorption rates follow Sb(V) > Hg(II), and the desorption rates follow reverse order. Applications of ethylene diamine tetraacetic acid (EDTA), Ca(II) and pH shocks affect desorption rates and desorbed quantities of Hg(II) from EPS-Hg complex. Temperature shock minimally affects the desorption rate of Hg(II). Conversely, the EPS-Sb complex is stable subjected to EDTA, Ca(II), temperature or pH shocks. The excitation-emission matrix (EEM) fluorescence spectroscopy and fast-Fourier (FT-IR) analysis showed that Hg(II) and Sb(V) principally interacted with polysaccharides and protein-like compounds in the EPS, respectively. The EPS-Hg complex presents a time bomb that may release high levels of Hg(II) in short time period under environmental shocks. PMID:23247408

  9. Thermal desorption: A technology review

    SciTech Connect

    Sullivan, T.P.

    1998-12-31

    The development of new and innovative technologies to treat hazardous waste is driven by the extreme costs associated with remediating contaminated sites. One innovative technology is thermal desorption, which heats soils, sediments, and sludges to volatilize contaminants present, then recovers the contaminants or destroys them. This paper discusses thermal desorption systems in detail, including evaluations of their performance, cost, and safety. The performance of thermal desorption units is determined by reviewing results of Superfund demonstration projects, remedial efforts, and pilot tests. These results indicate that thermal desorption is able to meet treatment standards for wastes contaminated with volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), polycyclic aromatic hydrocarbons (PAHs), fuels, and polychlorinated biphenyls (PCBs). Additionally, thermal desorption is competitive from a cost standpoint, with low temperature thermal desorption among the least expensive remediation technologies and high temperature thermal desorption in the middle of the cost band. The final aspect of thermal desorption discussed is worker exposure from both stack emissions and fugitive emissions. Air contaminant modeling was used to estimate ambient contaminant concentrations based on stack emission limits from previous remedial efforts. These estimates were compared with the American Conference of Governmental Industrial Hygienists (ACGIH) Threshold Limit Values (TLVs) and the OSHA Permissible Exposure Limits (PELs). Through this comparison, it was determined that, if the stack emissions limits are not exceeded, the ambient contaminant concentrations ranged from one order to seven orders of magnitude below the exposure standards.

  10. Microscopic Model of Associative Desorption for Hydrogen on Mo(110)

    NASA Astrophysics Data System (ADS)

    Yakovkin, I. N.; Osovskii, V. D.; Petrova, N. V.; Ptushinskii, Yu. G.

    Adsorbed hydrogen layers on the Mo(110) surface have been investigated both experimentally by temperature programmed desorption (TPD) method and theoretically by means of DFT-based optimization of surface structures. We suggest a novel microscopic model of the associative hydrogen desorption, which explains essential features of the process. In this model, the process of hydrogen desorption can be described as association of hydrogen atoms on the surface, but molecular formation is actually accomplished while the molecule moves away from the surface. We also suggest a new algorithm for realistic Monte Carlo simulations of associative desorption, which implements the microscopic description of the association of hydrogen adatoms into a molecule with activation energy, found from the DFT calculations. Good agreement between simulated and experimental TPD spectra gives insight into different behavior of the spectra, obtained for low and high hydrogen coverages on the Mo(110) surface.

  11. Waste Isolation Safety Assessment Program. Task 4. Third Contractor Information Meeting. [Adsorption-desorption on geological media

    SciTech Connect

    Not Available

    1980-06-01

    The study subject of this meeting was the adsorption and desorption of radionuclides on geologic media under repository conditions. This volume contans eight papers. Separate abstracts were prepared for all eight papers. (DLC)

  12. Water desorption from nanostructured graphite surfaces.

    PubMed

    Clemens, Anna; Hellberg, Lars; Grnbeck, Henrik; Chakarov, Dinko

    2013-12-21

    Water interaction with nanostructured graphite surfaces is strongly dependent on the surface morphology. In this work, temperature programmed desorption (TPD) in combination with quadrupole mass spectrometry (QMS) has been used to study water ice desorption from a nanostructured graphite surface. This model surface was fabricated by hole-mask colloidal lithography (HCL) along with oxygen plasma etching and consists of a rough carbon surface covered by well defined structures of highly oriented pyrolytic graphite (HOPG). The results are compared with those from pristine HOPG and a rough (oxygen plasma etched) carbon surface without graphite nanostructures. The samples were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TPD experiments were conducted for H2O coverages obtained after exposures between 0.2 and 55 langmuir (L) and reveal a complex desorption behaviour. The spectra from the nanostructured surface show additional, coverage dependent desorption peaks. They are assigned to water bound in two-dimensional (2D) and three-dimensional (3D) hydrogen-bonded networks, defect-bound water, and to water intercalated into the graphite structures. The intercalation is more pronounced for the nanostructured graphite surface in comparison to HOPG surfaces because of a higher concentration of intersheet openings. From the TPD spectra, the desorption energies for water bound in 2D and 3D (multilayer) networks were determined to be 0.32 0.06 and 0.41 0.03 eV per molecule, respectively. An upper limit for the desorption energy for defect-bound water was estimated to be 1 eV per molecule. PMID:24018989

  13. Oxygen sorption and desorption properties of selected lanthanum manganites and lanthanum ferrite manganites.

    PubMed

    Nielsen, Jimmi; Skou, Eivind M; Jacobsen, Torben

    2015-06-01

    Temperature-programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid-oxide fuel cell (SOFC) cathode materials (La(0.85) Sr(0.15)0.95 MnO(3+?) (LSM) and La(0.60) Sr(0.40) Fe(0.80) Mn(0.20) O(3-?) (LSFM). The powders were characterized by X-ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second-order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate-determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re-adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order. PMID:25784205

  14. Ultra high vacuum high precision low background setup with temperature control for thermal desorption mass spectroscopy (TDA-MS) of hydrogen in metals.

    PubMed

    Merzlikin, Sergiy V; Borodin, S; Vogel, D; Rohwerder, M

    2015-05-01

    In this work, a newly developed UHV-based high precision low background setup for hydrogen thermal desorption analysis (TDA) of metallic samples is presented. Using an infrared heating with a low thermal capacity enables a precise control of the temperature and rapid cool down of the measurement chamber. This novel TDA-set up is superior in sensitivity to almost every standard hydrogen analyzer available commercially due to the special design of the measurement chamber, resulting in a very low hydrogen background. No effects of background drift characteristic as for carrier gas based TDA instruments were observed, ensuring linearity and reproducibility of the analysis. This setup will prove to be valuable for detailed investigations of hydrogen trapping sites in steels and other alloys. With a determined limit of detection of 5.9×10(-3)µg g(-1) hydrogen the developed instrument is able to determine extremely low hydrogen amounts even at very low hydrogen desorption rates. This work clearly demonstrates the great potential of ultra-high vacuum thermal desorption mass spectroscopy instrumentation. PMID:25702992

  15. Probing Electron Transfer Dynamics at MgO Surfaces by Mg-Atom Desorption

    SciTech Connect

    Joly, Alan G.; Henyk, Matthias; Beck, Kenneth M.; Trevisanutto, P. E.; Sushko, Petr V.; Hess, Wayne P.; Shluger, Alexander L.

    2006-08-14

    Desorption of a weakly bound adsorbate from a porous solid was studied for the case of N2 on amorphous solid water (ASW). Porous ASW films of different thickness were grown on Pt(111) by ballistic deposition. N2 adsorption and desorption kinetics were monitored mass-spectrometrically. Temperature programmed desorption spectra show that with the increasing film thickness, the N2 desorption peak systematically shifts to higher temperatures. The results are explained and quantitatively reproduced by a simple model, which assumes that the N2 transport within the film is faster than the depletion rate to vacuum. The local coverage at the pore mouth determines the desorption rate. For thick ASW films (>1 ?m), the assumption of the fast equilibration within the film is shown to be no longer valid due to diffusion limitations. The mechanisms of the adsorbate transport are discussed.

  16. A New Cold-Bore Experiment for Heavy-Ion Induced Molecular Desorption Studies at Low Temperatures: First Results obtained at 300 K, 77 K, and 15 K

    NASA Astrophysics Data System (ADS)

    Mahner, E.; Bender, M.; Kollmus, H.

    2005-06-01

    A dedicated cold-bore ion desorption experiment was performed in August 2004 at CERN's Heavy Ion Accelerator LINAC 3. The dynamic outgassing of 4.2 MeV/u Pb53+ ions, impacting under 89.2° grazing incidence onto a copper tube, was studied as a function of the target temperature. Partial pressure rises of H2, CH4, CO, CO2, H2O, and O2 were measured at 300 K, 77 K, and 15 K using continuous lead ion bombardment. The new experimental setup is described and first pressure rise measurements are presented.

  17. Characterization of Biochar using Temperature Programmed Oxidation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biochar from the fast pyrolysis of biomass was characterized by Temperature Programmed Oxidation. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. The samples examined include soy and barley...

  18. Electron stimulated molecular desorption of a non-evaporable Zr-V-Fe alloy getter at room temperature

    NASA Astrophysics Data System (ADS)

    Le Pimpec, F.; Grbner, O.; Laurent, J. M.

    2002-10-01

    Electron stimulated molecular desorption (ESD) from a non-evaporable getters (NEG) St 707 (SAES Getters ) sample after conditioning and after saturation with isotopic carbon monoxide (cf. nomenclature in Handbook of Chemistry and Physics, CRC Press, 1994), 13C 18O, 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 1.610 15 electrons s -1. The electrons were impinging on the 15 cm 2 target surface at perpendicular incidence. It is found that the desorption yields ? (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 13C 18O are lower than for OFHC copper baked at 120 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 accessible to ESD.

  19. Cyclic CO2 chemisorption-desorption behavior of Na2ZrO3: Structural, microstructural and kinetic variations produced as a function of temperature

    NASA Astrophysics Data System (ADS)

    Martnez-dlCruz, Lorena; Pfeiffer, Heriberto

    2013-08-01

    A structural, microstructural and kinetic analysis of the Na2ZrO3-CO2 system was performed over 20 chemisorption-desorption cycles. Different cyclic experiments were performed between 500 and 800 C. Although the best results were obtained in Na2ZrO3 sample treated at 550 C, all the samples treated between 500 and 700 C presented good CO2 chemisorption efficiencies and stabilities. On the contrary, Na2ZrO3 sample treated at 800 C presented a continuous decrement of the CO2 chemisorption. After 20 cycles all the samples presented a partial Na2ZrO3 decomposition, determined by the ZrO2 formation, which was associated to sodium sublimation. Additionally, the Na2ZrO3 microstructural analysis showed a systematic morphological evolution. It was microscopically observed that Na2ZrO3 particles tend to fracture due to the Na2CO3 formation. Later, after several cycles these tiny fractured particles sinter producing new polyhedral and dense Na2ZrO3-ZrO2 particles. Finally, an exhaustive kinetic analysis showed a high CO2 chemisorption-desorption stability at different temperatures.

  20. Indium nitride surface structure, desorption kinetics and thermal stability

    NASA Astrophysics Data System (ADS)

    Acharya, Ananta

    Unique physical properties such as small effective mass, high electron drift velocities, high electron mobility and small band gap energy make InN a candidate for applications in high-speed microelectronic and optoelectronic devices. The aim of this research is to understand the surface properties, desorption kinetics and thermal stability of InN epilayers that affect the growth processes and determine film quality as well as device performance and life time. We have investigated the structural properties, the surface desorption kinetics, and the thermal stability using Auger electron spectroscopy (AES), x-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM), high resolution electron energy loss spectroscopy (HREELS), and temperature programmed desorption (TPD). Investigations on high pressure chemical vapor deposition (HPCVD)-grown InN samples revealed the presence of tilted crystallites, which were attributed to high group V/III flux ratio and lattice mismatch. A study of the thermal stability of HPCVD-grown InN epilayers revealed that the activation energy for nitrogen desorption was 1.6+/-0.2 eV, independent of the group V/III flux ratio. Initial investigations on the ternary alloy In0.96Ga0.04N showed single-phase, N-polar epilayers using XRD and HREELS, while a thermal desorption study revealed an activation energy for nitrogen desorption of 1.14 +/- 0.06 eV. HREELS investigations of atomic layer epitaxy (ALE)-grown InN revealed vibrational modes assigned to N-N vibrations. The atomic hydrogen cleaned InN surface also exhibited modes assigned to surface N-H without showing In-H species, which indicated N-polar InN. Complete desorption of hydrogen from the InN surface was best described by the first-order desorption kinetics with an activation energy of 0.88 +/- 0.06 eV and pre-exponential factor of (1.5 +/- 0.5) x105 s-1. Overall, we have used a number of techniques to characterize the structure, surface bonding configuration, thermal stability and hydrogen desorption kinetics of InN and In0.96Ga0.04N epilayers grown by HPCVD and ALE. High group V/III precursors ratio and lattice mismatch have a crucial influence on the film orientation. The effects of hydrogen on the decomposition add to the wide variation in the activation energy of nitrogen desorption. Presence of surface defects lowers the activation energy for hydrogen desorption from the surface.

  1. Study of hydrogen desorption from gallium nitride(0001)

    NASA Astrophysics Data System (ADS)

    Yang, Yong

    2002-09-01

    Earlier work from this lab investigated interaction of hydrogen with GaN(0001) by surface science techniques such as low energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss spectroscopy (ELS or EELS) and high resolution electron energy loss spectroscopy (HREELS). Based on these, we perform temperature programmed desorption (TPD) and electron stimulated desorption (ESD) studies on the surface. A significant part of this dissertation work has been the design and construction of an ultra-high vacuum (UHV) apparatus, gas manifold system, sample mount, e-beam heater, wide spot electron gun, ion gun and differentially-pumped mass spectrometry system. Therefore, this dissertation also includes a description of the state of the art apparatus which was constructed to perform the experiments described in this work. TPD of deuterium on GaN(0001) from Ga sites has been performed to measure the desorption kinetic parameters and to further understand the desorption mechanism. For a heating rate of 1C/s, the main feature peaks at 410C while the smaller feature occurs as a shoulder near 320C. The ratio between the intensity of the main desorption peak and shoulder gets larger after more sputtering and annealing cycles. Heating rate variation analysis indicates a pseudo-first-order pre-exponential factor of 1 x 106 s-1 and desorption activation energy of 1.1 eV. The values are believed to be too low and attributed to multiple surface sites. Assuming a pre-exponential factor of 1 x 1013 s-1 yields an activation energy of 2.0 eV which implies a value for the molecular hydrogen adsorption barrier of 0.9 eV. After the deuterated sample being exposed to various doses of 90-eV electrons, TPD shows a decrease in the flux of desorbing deuterium centers at 400C. This reduction in deuterium desorption is attributed to removal of surface D via electron stimulated desorption (ESD). The peak desorption temperature does not shift as hydrogen is removed by ESD indicating first order desorption and a diffusion mechanism is proposed. From the area under the TPD curves, an ESD cross-section of 9 x 10-19 cm2 is estimated. (Abstract shortened by UMI.)

  2. Program predicts reservoir temperature and geothermal gradient

    SciTech Connect

    Kutasov, I.M.

    1992-06-01

    This paper reports that a Fortran computer program has been developed to determine static formation temperatures (SFT) and geothermal gradient (GG). A minimum of input data (only two shut-in temperature logs) is required to obtain the values of SFT and GG. Modeling of primary oil production and designing enhanced oil recovery (EOR) projects requires knowing the undisturbed (static) reservoir temperature. Furthermore, the bottom hole circulating temperature (BHCT) is an important factor affecting a cement's thickening time, rheological properties, compressive strength, development, and set time. To estimate the values of BHCT, the geothermal gradient should be determined with accuracy. Recently we obtained an approximate analytical solution which describes the shut-in temperature behavior.

  3. Low-Cost Programmed Oven Temperature Controller.

    ERIC Educational Resources Information Center

    Clubine, Gerald D.

    1982-01-01

    A remote, programed oven temperature controller unit was built for about $425.00. Specifications, circuit diagrams, design details, and operations are discussed. Detailed information including complete schematics, parts list, and detailed theory of operation may be obtained by contacting the author. (Author/SK)

  4. Investigation of mechanisms contributing to slow desorption of hydrophobic organic compounds from mineral solids

    SciTech Connect

    Farrell, J.; Grassian, D.; Jones, M.

    1999-04-15

    Predicting the transport and fate of hydrophobic organic contaminants in underground aquifers requires a mechanistic understanding of sediment-contaminant interactions. This research investigates the mechanisms contributing to the slow desorption of hydrophobic organic compounds from water-saturated mineral solids. The mechanisms investigated were adsorption-retarded aqueous diffusion, micropore diffusion, high-energy micropore adsorption, and micropore blockage by precipitated minerals. To reduce the potential confounding effects of adsorbent heterogeneity, a set of homogeneous silica gel and glass bead adsorbents were used in the investigation. Desorption rates for the slow-desorbing fractions of chloroform (CF), trichloroethylene (TCE), and perchloroethylene (PCE) from silica gel did not conform to the pore-diffusion model for adsorption-retarded aqueous diffusion. This indicated that diffusion through adsorbent mesopores was not responsible for slow desorption from silica gel. Micropore-diffusion modeling of TCE desorption from three silica gels and microporous glass beads indicated that pores less than 2 nm in diameter were responsible for slow desorption. Desorption rates of CF, TCE, and PCE from silica gel were also measured in methanol solutions. Under methanol extraction conditions, desorption rates for all three compounds were 1--2 orders of magnitude less than under water-saturated conditions. The activation energy for TCE desorption from water-saturated silica gel was measured using temperature-programmed desorption. The TCE desorption activation energy of 15 kJ/mol was close to the dissolution enthalpy for silica gel of 13 kJ/mol. This supported the hypothesis that micropore blockage by precipitated minerals may be limiting contaminant desorption rates under water-saturated conditions.

  5. Low-Temperature Power Electronics Program

    NASA Technical Reports Server (NTRS)

    Patterson, Richard L.; Dickman, John E.; Hammoud, Ahmad; Gerber, Scott

    1997-01-01

    Many space and some terrestrial applications would benefit from the availability of low-temperature electronics. Exploration missions to the outer planets, Earth-orbiting and deep-space probes, and communications satellites are examples of space applications which operate in low-temperature environments. Space probes deployed near Pluto must operate in temperatures as low as -229 C. Figure 1 depicts the average temperature of a space probe warmed by the sun for various locations throughout the solar system. Terrestrial applications where components and systems must operate in low-temperature environments include cryogenic instrumentation, superconducting magnetic energy storage, magnetic levitation transportation system, and arctic exploration. The development of electrical power systems capable of extremely low-temperature operation represents a key element of some advanced space power systems. The Low-Temperature Power Electronics Program at NASA Lewis Research Center focuses on the design, fabrication, and characterization of low-temperature power systems and the development of supporting technologies for low-temperature operations such as dielectric and insulating materials, power components, optoelectronic components, and packaging and integration of devices, components, and systems.

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

    SciTech Connect

    King, Sean W. Tanaka, Satoru; Davis, Robert F.; Nemanich, Robert J.

    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 Si–O bonding, they may still exhibit significant chemical reactivity due to the creation of surface dangling bonds resulting from H{sub 2} desorption from previously undetected silicon hydride and surface hydroxide species.

  7. Kinetic compensation effect in thermal desorption

    NASA Astrophysics Data System (ADS)

    Zuniga-Hansen, Nayeli; Silbert, Leonardo E.; Calbi, Mercedes

    The parameters which characterize the rates of many thermally activated processes are often extracted using the Arrhenius equation. A series of closely related thermally activated processes exhibit systematic variations in the energies of activation, Ea, and preexponential factor, ?, in response to a perturbation, which leads to the concept of `kinetic compensation', such that the different parameters in the Arrhenius equation balance each other out thereby leading to an implicitly assumed constant rate. However, the compensation effect has not been generally demonstrated and its origins are not completely understood. Using kinetic Monte Carlo simulations on a model interface, we explore how site-adsorbate and adsorbate-adsorbate interactions, and surface structural changes influence surface coverage and the kinetic parameters during a typical temperature programmed desorption process. We find that the concept of the compensation effect for interacting species breaks down and the time characterizing desorption increases with increasing interaction strength due to an increase in the effective activation energy. At the `molecular' level the changes are the result of enhanced site correlations with increasing adsorbate interaction strength suppressing the onset of desorption.

  8. ENGINEERING BULLETIN: THERMAL DESORPTION TREATMENT

    EPA Science Inventory

    Thermal desorption is an EX SITU means to physically separate volatile and some semivolatile contaminants from soil, sediments, sludge, and filter cakes by heating them at temperatures high enough to volatilize the organic contaminants. or wastes containing up to 10 percent organ...

  9. ENGINEERING BULLETIN: THERMAL DESORPTION TREATMENT.

    EPA Science Inventory

    Thermal desorption is an EX SITU means to physically separate volatile and some semivolatile contaminants from soil, sediments, sludge, and filter cakes by heating them at temperatures high enough to volatilize the organic contaminants. For wastes containing up to 10 percent orga...

  10. Effects of Varied pH, Growth Rate and Temperature using Controlled fermentation and Batch culture on Matrix Assisted Laser Desorption/Ionization Whole Cell Protein Fingerprints.

    SciTech Connect

    Wunschel, David S.; Hill, Eric A.; Mclean, Jeffrey S.; Jarman, Kristin H.; Gorby, Yuri A.; Valentine, Nancy B.; Wahl, Karen L.

    2005-09-01

    Rapid identification of microorganisms using matrix assisted laser desorption/ionization (MALDI) is a rapidly growing area of research due to the minimal sample preparation, speed of analysis and broad applicability of the technique. This approach relies on protein markers to identify microorganisms. Therefore, variations in culture conditions that affect protein expression may limit the ability of MALDI-MS to correctly identify an organism. We have expanded our efforts to investigate the effects of culture conditions on MALDI-MS protein signatures to examine the effects of pH, growth rate and temperature. Continuous cultures maintained in bioreactors were used to maintain specific growth rates and pH for E. coli HB 101. Despite measurable morphological differences between growth conditions, the MALDI-MS data associated each culture with the appropriate library entry (E. coli HB 101 generated using batch culture on a LB media), independent of pH or growth rate. The lone exception was for a biofilm sample collected from one of the reactors which had no appreciable degree of association with the correct library entry. Within the data set for planktonic organisms, variations in growth rate created the largest variation between fingerprints. The effect of varying growth temperature on Y. enterocolitica was also examined. While the anticipated effects on phenotype were observed, the MALDI-MS technique provided the proper identification.

  11. The release of trapped gases from amorphous solid water films. II. ``Bottom-up'' induced desorption pathways

    NASA Astrophysics Data System (ADS)

    Alan May, R.; Scott Smith, R.; Kay, Bruce D.

    2013-03-01

    In this (Paper II) and the preceding companion paper (Paper I; R. May, R. Smith, and B. Kay, J. Chem. Phys. 138, 104501 (2013), 10.1063/1.4793311), we investigate the mechanisms for the release of trapped gases from underneath amorphous solid water (ASW) films. In Paper I, we focused on the low coverage regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime, the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Paper I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that these abrupt desorption bursts are due to pressure induced structural failure of the ASW overlayer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores formed during ASW deposition. The extent of desorption and the line shape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of ASW is used to vary the porosity of the overlayer and strongly supports the hypothesis that the low temperature desorption pathway is due to porosity that is templated into the ASW overlayer by the underlayer during deposition.

  12. The Release of Trapped Gases from Amorphous Solid Water Films: II. Bottom-Up Induced Desorption Pathways

    SciTech Connect

    May, Robert A.; Smith, R. Scott; Kay, Bruce D.

    2013-03-14

    In this (Paper II) and the preceding companion paper (Paper I) we investigate the mechanisms for the release of trapped gases from underneath of amorphous solid water (ASW) films. In Paper I, we focused on the low coverage (pressure) regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage (pressure) regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Paper I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that abrupt desorption bursts are due to pressure induced structural failure of the ASW overlyaer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores and connected pathways formed during ASW deposition. The extent of desorption and the lineshape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of the ASW is used vary the porosity of overlayer and confirm that the low temperature desorption pathway is due to porosity that is inherent in the ASW overlayer during deposition.

  13. Desorption of a two-state system: Laser probing of gallium atom spin-orbit states from silicon (100)

    NASA Astrophysics Data System (ADS)

    Carleton, Karen L.; Bourguignon, Bernard; Leone, Stephen R.

    The interactions of gallium atom spin-orbit states with silicon (100) surfaces are studied by temperature programmed desorption (TPD) using laser-induced fluorescence detection. State-resolved sticking coefficients are measured and are found to be unity for both spin-orbit states ( 2P{1}/{2}, 2P{3}/{2}, ?E = 2.5 kcal mol-1, 10.5 kJ mol-1) up to surface temperatures of 1000 K. A Redhead analysis of the state-specific TPD spectra yields essentially identical energies and pre-exponential factors for both spin-orbit states. A statistical branching ratio is observed between the 2P {1}/{2} and 2P {3}/{2} Ga states at the peak of the TPD curves. These results may be accounted for by a rapid interconversion between the two states during the desorption. Since the spin-orbit splitting in this case is small, a rapid interconversion may be anticipated; however, modeling the desorption kinetics yields important features for the desorption of a two-state system. The model shows that the Redhead analysis is not adequate to measure the desorption kinetic parameters of the individual states. The TPD spectra of the two states differ only very slightly because their shape is mainly controlled by the overall rate of desorption for the sum of the two channels. The population ratio between the states allows a direct comparison of the desorption energetics of the two channels. Errors of 5-10 kcal mol -1 can occur in a determination of the desorption energy of a hypothetical, slowly desorbing state if the presence of a rapid desorption channel is ignored. The model can be generalized to describe any multiple channel surface process, including multi-state desorption of the competition between desorption and diffusion into the bulk. These results are of interest in the epitaxial growth of GaAs on Si(100).

  14. Interfacial chemistry of a perfluoropolyether lubricant studied by X-ray photoelectron spectroscopy and temperature desorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Jones, William R., Jr.; Pepper, Stephen V.

    1993-01-01

    The interfacial chemistry of Fomblin Z25, a commercial perfluoropolyether used as lubricant for space applications was studied with different metallic surfaces: 440C steel, gold, and aluminum. Thin layers of Fomblin Z25 were evaporated onto the oxide-free substrates, and the interfacial chemistry was studied using XPS and TDS. The reactions were induced by heating the substrate and by rubbing the substrate with a steel ball. Gold was found to be completely unreactive towards Fomblin at any temperature. Reaction at room temperature was observed only in the case of the aluminum substrate, the most reactive towards Fomblin Z25 of the substrates studied. It was necessary to heat the 440C steel substrate to 190 C to induce decomposition of the fluid. The degradation of the fluid was indicated by the formation of a debris layer at the interface. This debris layer, composed of inorganic and organic reaction products, when completely formed, passivated the surface from further attack to the Fromblin on top. The tribologically induced reactions on 440C steel formed a debris layer of similar chemical characteristics to the thermally induced layer. In all cases, the degradation reaction resulted in preferential consumption of the difluoroformyl carbon (-OCF2O-).

  15. Desorption from interstellar ices

    NASA Astrophysics Data System (ADS)

    Roberts, J. F.; Rawlings, J. M. C.; Viti, S.; Williams, D. A.

    2007-12-01

    The desorption of molecular species from ice mantles back into the gas phase in molecular clouds results from a variety of very poorly understood processes. We have investigated three mechanisms: desorption resulting from H2 formation on grains, direct cosmic ray heating and cosmic ray-induced photodesorption. Whilst qualitative differences exist between these processes (essentially deriving from the assumptions concerning the species selectivity of the desorption and the assumed threshold adsorption energies, Et), all the three processes are found to be potentially very significant in dark cloud conditions. It is therefore important that all three mechanisms should be considered in studies of molecular clouds in which freeze-out and desorption are believed to be important. Employing a chemical model of a typical static molecular core and using likely estimates for the quantum yields of the three processes, we find that desorption by H2 formation probably dominates over the other two mechanisms. However, the physics of the desorption processes and the nature of the dust grains and ice mantles are very poorly constrained. We therefore conclude that the best approach is to set empirical constraints on the desorption, based on observed molecular depletions - rather than try to establish the desorption efficiencies from purely theoretical considerations. Applying this method to one such object (L1689B) yields upper limits to the desorption efficiencies that are consistent with our understanding of these mechanisms.

  16. The NASA high temperature superconductivity program

    NASA Technical Reports Server (NTRS)

    Sokoloski, Martin M.; Romanofsky, Robert R.

    1990-01-01

    It has been recognized from the onset that high temperature superconductivity held great promise for major advances across a broad range of NASA interests. The current effort is organized around four key areas: communications and data, sensors and cryogenics, propulsion and power, and space materials technology. Recently, laser ablated YBa2Cu3O(7-x) films on LaAIO produced far superior RF characteristics when compared to metallic films on the same substrate. This achievement has enabled a number of unique microwave device applications, such as low insertion loss phase shifters and high Q filters. Melt texturing and melt quenched techniques are being used to produce bulk materials with optimized magnetic properties. These yttrium enriched materials possess enhanced flux pinning characteristics and will lead to prototype cryocooler bearings. Significant progress has also occurred in bolometer and current lead technology. Studies are being conducted to evaluate the effect of high temperature superconducting materials on the performance and life of high power magneto-plasma-dynamic thrusters. Extended studies were also performed to evaluate the benefit of superconducting magnetic energy storage for LEO space station, lunar and Mars mission applications. The project direction and level of effort of the program are also described.

  17. Glycolaldehyde, methyl formate and acetic acid adsorption and thermal desorption from interstellar ices

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Brown, Wendy A.; Woods, Paul M.; Viti, Serena; Slater, Ben

    2015-02-01

    We have undertaken a detailed investigation of the adsorption, desorption and thermal processing of the astrobiologically significant isomers glycolaldehyde, acetic acid and methyl formate. Here, we present the results of laboratory infrared and temperature programmed desorption (TPD) studies of the three isomers from model interstellar ices adsorbed on a carbonaceous dust grain analogue surface. Laboratory infrared data show that the isomers can be clearly distinguished on the basis of their infrared spectra, which has implications for observations of interstellar ice spectra. Laboratory TPD data also show that the three isomers can be distinguished on the basis of their thermal desorption behaviour. In particular, TPD data show that the isomers cannot be treated the same way in astrophysical models of desorption. The desorption of glycolaldehyde and acetic acid from water-dominated ices is very similar, with desorption being mainly dictated by water ice. However, methyl formate also desorbs from the surface of the ice, as a pure desorption feature, and therefore desorbs at a lower temperature than the other two isomers. This is more clearly indicated by models of the desorption on astrophysical time-scales corresponding to the heating rate of 25 and 5 M⊙ stars. For a 25 M⊙ star, our model shows that a proportion of the methyl formate can be found in the gas phase at earlier times compared to glycolaldehyde and acetic acid. This has implications for the observation and detection of these molecules, and potentially explains why methyl formate has been observed in a wider range of astrophysical environments than the other two isomers.

  18. Particle-scale investigation of PAH desorption kinetics and thermodynamics from sediment.

    PubMed

    Ghosh, U; Talley, J W; Luthy, R G

    2001-09-01

    Dredged sediment from Milwaukee Harbor showed two primary classes of particles in the <2 mm size range: a lighter-density coal- and wood-derived fraction with 62% of total PAHs and a heavier-density sand, silt, and clay fraction containing the remaining 38% of the PAHs. Room-temperature PAH desorption kinetic studies on separated sediment fractions revealed slow desorption rates for the coal-derived particles and fast desorption rates for the clay/silt particles. The effect of temperature on PAH release was measured by thermal program desorption mass spectrometry to investigate the desorption activation energies for PAHs on the different sediment particles. Three activated diffusion-based models and an activated first-order rate model were used to describe the thermal desorption of PAHs for four molecular weight classes. PAH binding with the coal-derived particles was associated with high activation energies, typically in the range of 115-139 kJ/mol. PAHs bound to the clay/silt material had much lower activation energy, i.e., in the range of 37-41 kJ/ mol for molecular weight 202. Among the desorption models tested, a spherical diffusion model with PAHs located like a rind on the outer 1-3 microm region best described the PAH thermal desorption response for coal-derived particles. This internal PAH distribution pattern on coalderived particles is based on prior direct measurement of PAH locations at the subparticle scale. These studies reveal that heterogeneous particle types in sediment exhibit much different amounts and binding of PAHs. PAHs associated with coal-derived particles aged over several decades in the field appear to be far from reaching an equilibrium sorption state due to the extremely slow diffusivities through the polymer-like coal matrix. These results provide an improved mechanistic perspective for the understanding of PAH mobility and bioavailability in sediments. PMID:11563648

  19. Monte Carlo evaluation of thermal desorption rates

    SciTech Connect

    Adams, J.E.; Doll, J.D.

    1981-05-01

    The recently reported method for computing thermal desorption rates via a Monte Carlo evaluation of the appropriate transition state theory expression (J. E. Adams and J. D. Doll, J. Chem. Phys. 74, 1467 (1980)) is extended, by the use of importance sampling, so as to generate the complete temperature dependence in a single calculation. We also describe a straightforward means of calculating the activation energy for the desorption process within the same Monte Carlo framework. The result obtained in this way represents, for the case of a simple desorptive event, an upper bound to the true value.

  20. THERMAL DESORPTION TREATMENT

    EPA Science Inventory

    Thermal desorption is an ex situ means to physically separate volatile and some semivolatile contaminants from soil, sediments, sludges, and filter cakes. or wastes containing up to 10% organics or less, thermal desorption can be used alone for site remediation. t also may find a...

  1. Hydrogen adsorption and desorption at the Pt(110)-(12) surface: experimental and theoretical study.

    PubMed

    Gudmundsdttir, Sigrdur; Sklason, Egill; Weststrate, Kees-Jan; Juurlink, Ludo; Jnsson, Hannes

    2013-05-01

    The interaction of hydrogen with the Pt(110)-(12) surface is studied using temperature programmed desorption (TPD) measurements and density functional theory (DFT) calculations. The ridges in this surface resemble edges between micro-facets of Pt nano-particle catalysts used for hydrogen evolution (HER) and hydrogen oxidation reactions (HOR). The binding energy and activation energy for desorption are found to depend strongly on hydrogen coverage. At low coverage, the strongest binding sites are found to be the low coordination bridge sites at the edge and this is shown to agree well with the He-atom interaction and work function change which have been reported previously. At higher hydrogen coverage, the higher coordination sites on the micro-facet and in the trough get populated. The simulated TPD spectra based on the DFT results are in close agreement with our experimental spectra and provide microscopic interpretation of the three measured peaks. The lowest temperature peak obtained from the surface with highest hydrogen coverage does not correspond to desorption directly from the weakest binding sites, the trough sites, but is due to desorption from the ridge sites, followed by subsequent, thermally activated rearrangement of the H-adatoms. The reason is low catalytic activity of the Pt-atoms at the trough sites and large reduction in the binding energy at the ridge sites at high coverage. The intermediate temperature peak corresponds to desorption from the micro-facet. The highest temperature peak again corresponds to desorption from the ridge sites, giving rise to a re-entrant mechanism for the thermal desorption. PMID:23518690

  2. Desorption and sublimation kinetics for fluorinated aluminum nitride surfaces

    SciTech Connect

    King, Sean W. Davis, Robert F.; Nemanich, Robert J.

    2014-09-01

    The adsorption and desorption of halogen and other gaseous species from surfaces is a key fundamental process for both wet chemical and dry plasma etch and clean processes utilized in nanoelectronic fabrication processes. Therefore, to increase the fundamental understanding of these processes with regard to aluminum nitride (AlN) surfaces, temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) have been utilized to investigate the desorption kinetics of water (H{sub 2}O), fluorine (F{sub 2}), hydrogen (H{sub 2}), hydrogen fluoride (HF), and other related species from aluminum nitride thin film surfaces treated with an aqueous solution of buffered hydrogen fluoride (BHF) diluted in methanol (CH{sub 3}OH). Pre-TPD XPS measurements of the CH{sub 3}OH:BHF treated AlN surfaces showed the presence of a variety of Al-F, N-F, Al-O, Al-OH, C-H, and C-O surfaces species in addition to Al-N bonding from the AlN thin film. The primary species observed desorbing from these same surfaces during TPD measurements included H{sub 2}, H{sub 2}O, HF, F{sub 2}, and CH{sub 3}OH with some evidence for nitrogen (N{sub 2}) and ammonia (NH{sub 3}) desorption as well. For H{sub 2}O, two desorption peaks with second order kinetics were observed at 195 and 460?C with activation energies (E{sub d}) of 51??3 and 87??5?kJ/mol, respectively. Desorption of HF similarly exhibited second order kinetics with a peak temperature of 475?C and E{sub d} of 110??5?kJ/mol. The TPD spectra for F{sub 2} exhibited two peaks at 485 and 585?C with second order kinetics and E{sub d} of 62??3 and 270??10?kJ/mol, respectively. These values are in excellent agreement with previous E{sub d} measurements for desorption of H{sub 2}O from SiO{sub 2} and AlF{sub x} from AlN surfaces, respectively. The F{sub 2} desorption is therefore attributed to fragmentation of AlF{sub x} species in the mass spectrometer ionizer. H{sub 2} desorption exhibited an additional high temperature peak at 910?C with E{sub d}?=?370??10?kJ/mol that is consistent with both the dehydrogenation of surface AlOH species and H{sub 2} assisted sublimation of AlN. Similarly, N{sub 2} exhibited a similar higher temperature desorption peak with E{sub d}?=?535??40?kJ/mol that is consistent with the activation energy for direct sublimation of AlN.

  3. Hydrogenation of CO-bearing species on grains: unexpected chemical desorption of CO

    NASA Astrophysics Data System (ADS)

    Minissale, M.; Moudens, A.; Baouche, S.; Chaabouni, H.; Dulieu, F.

    2016-02-01

    The amount of methanol in the gas phase and the CO depletion from the gas phase are still open problems in astrophysics. In this work, we investigate solid state hydrogenation of CO-bearing species via H-exposure of carbon monoxide, formaldehyde, and methanol thin films deposited on cold surfaces, paying attention to the possibility of a return to the gas phase. The products are probed via infrared spectroscopy (RAIRS), and two types of mass spectroscopy protocols: temperature-programmed desorption (TPD), and during-exposure desorption (DED) techniques. In the case of the [CO+H] reactive system, we have found that chemical desorption of CO is more efficient than H-addition reactions and HCO and H2CO formation; the studies of the [H2CO +H] reactive system show a strong competition between all surface processes, chemical desorption of H2CO, H-addition (CH3OH formation) and H-abstraction (CO formation); finally, [CH3OH +H] seems to be a non-reactive system and chemical desorption of methanol is not efficient. CO-bearing species present a see-saw mechanism between CO and H2CO balanced by the competition of H-addition and H2 abstraction that enhances the CO chemical desorption. The chemical network leading to methanol has to be reconsidered. The methanol formation on the surface of interstellar dust grain is still possible through CO+H reaction; nevertheless its consumption of adsorbed H atoms should be higher than previously expected.

  4. Study of the Thermal Decomposition of Some Components of Biomass by Desorption Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Palianytsia, Borys; Kulik, Tetiana; Dudik, Olesia; Cherniavska, Tetiana; Tonkha, Oksana

    The investigation of thermal transformations of lignin samples have been carried out using temperature programmed desorption mass spectrometry method (TPD-MS). Main stages and products of lignin pyrolysis have been identified. The first stages (Tmax = 230 C and Tmax = 300 C) are attributed to thermal transformations of lignin peripheral polysaccharide fragments such as hemicellulose and cellulose respectively. The second stage (Tmax = 335 C) is associated with desorption of lignin structural elements in the molecular forms as a result of depolymerization processes of polymeric blocks of lignin. The third stage (Tmax = 370 C) correspond to a deeper decomposition of lignin and characterized by desorption of smaller structural fragments in molecular forms (m/z = 110, pyrocatechol). Pressure-temperature curves of pyrolysis of lignin samples have been analyzed.

  5. Segregation of O2 and CO on the surface of dust grains determines the desorption energy of O2

    NASA Astrophysics Data System (ADS)

    Noble, J. A.; Diana, S.; Dulieu, F.

    2015-12-01

    Selective depletion towards pre-stellar cores is still not understood. The exchange between the solid and gas phases is central to this mystery. The aim of this paper is to show that the thermal desorption of O2 and CO from a submonolayer mixture is greatly affected by the composition of the initial surface population. We have performed thermally programmed desorption (TPD) experiments on various submonolayer mixtures of O2 and CO. Pure O2 and CO exhibit almost the same desorption behaviour, but their desorption differs strongly when mixed. Pure O2 is slightly less volatile than CO, while in mixtures, O2 desorbs earlier than CO. We analyse our data using a desorption law linking competition for binding sites with desorption, based on the assumption that the binding energy distribution of both molecules is the same. We apply Fermi-Dirac statistics in order to calculate the adsorption site population distribution, and derive the desorbing fluxes. Despite its simplicity, the model reproduces the observed desorption profiles, indicating that competition for adsorption sites is the reason for lower temperature O2 desorption. CO molecules push-out or `dislodge' O2 molecules from the most favourable binding sites, ultimately forcing their early desorption. It is crucial to consider the surface coverage of dust grains in any description of desorption. Competition for access to binding sites results in some important discrepancies between similar kinds of molecules, such as CO and O2. This is an important phenomenon to be investigated in order to develop a better understanding of the apparently selective depletion observed in dark molecular clouds.

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

    SciTech Connect

    Bartram, Michael E.; Creighton, J. Randall

    1999-05-26

    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, N15H3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N2 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.

  7. Effect of Rh particle size on CO desorption from Rh/alumina model catalysts

    NASA Astrophysics Data System (ADS)

    Belton, David N.; Schmieg, Steven J.

    1988-08-01

    The adsorption of CO on small Rh particles on oxidized Al(100) was studied using temperature programmed desorption (TPD) and Auger electron spectroscopy (AES). The desorption data for CO were obtained for two {Rh}/{Al 2O 3} samples as well as for Rh(111). The supported Rh model catalysts were prepared from thermal decomposition of [Rh(CO 2Cl] 2 on an oxidized Al(100) substrate. By varying the substrate temperature and the amount of deposited Rh, samples were prepared with average Rh particles sizes of 20 and 70 . TPD data from the 70 Rh particles were similar to that from Rh(111), with a major peak at 500 K and a shoulder at 400 K for a saturation CO exposure. TPD from the small particles was very different from Rh(111) and the larger particles, showing a single broad peak centered at 415 K. The data show a particle size effect for the desorption on CO from supported Rh. Redhead analysis of the data for first-order desorption gave an activation energy of 30 kcal/mol for all of the samples at low CO coverages. A more detailed analysis using peak widths and peak temperatures was also performed. These calculations gave a very low activation energy, 19.8 kcal/mol, and preexponential, 110 8{cm2}/{s} for the small particles. These very low values were interpreted to mean that multiple desorption states, mobile precursors, or coverage dependent activation energies were affecting the data from the small particles. Calculations of first-order desorption rates showed that desorption states different than those on Rh(111) are the dominant species on the small particles at high CO coverages.

  8. Evaluation of biochars by temperature programmed oxidation/mass spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biochar from the thermochemical conversion of biomass was evaluated by Temperature Programmed Oxidation (TPO) coupled with mass spectroscopy. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. ...

  9. Molecular desorption of a nonevaporable getter St 707 irradiated at room temperature with synchrotron radiation of 194 eV critical photon energy

    NASA Astrophysics Data System (ADS)

    Le Pimpec, F.; Grbner, O.; Laurent, J. M.

    2003-05-01

    Photon stimulated molecular desorption from a nonevaporable getter (NEG) St 707 (SAES Getters) surface after conditioning and after saturation with isotopic carbon monoxide [cf. nomenclature in Handbook of Chemistry and Physics, 74th edition, edited by D. R. Lide (CRC Press, Boca Raton, 1994)] 13C18O, has been studied on a dedicated beamline at the EPA ring at CERN. The synchrotron radiation of 194 eV critical energy and with an average photon intensity of ~11017 photons s-1 was impinging on the sample at perpendicular incidence. It is found that the desorption yields ? (molecules/photon) of the characteristic gases in an UHV system (hydrogen, methane, carbon monoxide, and carbon dioxide) for a freshly activated NEG and for a NEG fully saturated with 13C18O are lower than that of 300 C baked stainless steel.

  10. Rapid screening of pharmaceutical drugs using thermal desorption - SALDI mass spectrometry

    NASA Astrophysics Data System (ADS)

    Grechnikov, A. A.; Kubasov, A. E.; Georgieva, V. B.; Borodkov, A. S.; Nikiforov, S. M.; Simanovsky, Ya O.; Alimpiev, S. S.

    2012-12-01

    A novel approach to the rapid screening of pharmaceutical drugs by surface assisted laser desorption-ionization (SALDI) mass spectrometry with the rotating ball interface coupled with temperature programmed thermal desorption has been developed. Analytes were thermally desorbed and deposited onto the surface of amorphous silicon substrate attached to the rotating ball. The ball was rotated and the deposited analytes were analyzed using SALDI. The effectiveness of coupling SALDI mass spectrometry with thermal desorption was evaluated by the direct and rapid analysis of tablets containing lidocaine, diphenhydramine and propranolol without any sample pretreatment. The overall duration of the screening procedure was 30÷40 sec. Real urine samples were studied for drug analysis. It is shown that with simple preparation steps, urine samples can be quantitatively analyzed using the proposed technique with the detection limits in the range of 0.2÷0.5 ng/ml.

  11. Desorption of n-alkanes from graphene: a van der Waals density functional study.

    PubMed

    Londero, Elisa; Karlson, Emma K; Landahl, Marcus; Ostrovskii, Dimitri; Rydberg, Jonatan D; Schrder, Elsebeth

    2012-10-24

    A recent study of temperature-programmed desorption (TPD) measurements of small linear alkane molecules (n-alkanes, with formula C(N)H(2N+2)) from C(0001) deposited on Pt(111) shows a linear relationship of the desorption energy with increasing n-alkane chain length N. We here present a van der Waals density functional study of the desorption barrier energy of the ten smallest n-alkanes (of carbon chain length N = 1-10) from graphene. We find linear scaling with N, including a non-zero intercept with the energy axis, i.e. an offset at the extrapolation to N = 0. This calculated offset is quantitatively similar to the results of the TPD measurements. From further calculations of the polyethylene polymer we offer a suggestion for the origin of the offset. PMID:23032797

  12. High temperature static strain sensor development program

    NASA Astrophysics Data System (ADS)

    Hulse, C.; Bailey, R.; Grant, H.

    1983-10-01

    Electrical resistance strain gages useful for static strain measurements on nickel or cobalt superalloy parts inside a gas turbine engine on a test stand are being developed. Measurements of this type are of great importance in meeting the goals of the HOST program because, without reliable knowledge of the stresses and strains which exist in specific components, it will be difficult to fully appreciate where improvements in design and materials can be implemented. The first part of the effort consisted of a strain gage alloy development program which will be followed by an investigation of complete strain gage systems which will use the best of the alloys developed together with other system improvements.

  13. Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory.

    PubMed

    Gao, Li; Pal, Partha Pratim; Seideman, Tamar; Guisinger, Nathan P; Guest, Jeffrey R

    2016-02-01

    Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionization induced by inelastic tunneling electrons. The observed current independence of the desorption yield suggests that the vibrational excitation is a single-electron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (?2 eV), as would be expected from the identified desorption mechanism. PMID:26787160

  14. High temperature static strain gage program

    NASA Astrophysics Data System (ADS)

    Hulse, C.; Bailey, R.; Grant, H.

    1984-10-01

    Development of electrical resistance strain gages for static strain measurements of nickel or cobalt superalloy parts inside a gas turbine engine on a test stand was inititated. Measurements of this type are of great importance because without reliable knowledge of the stresses and strains which exist in specific components, it will be difficult to fully appreciate where improvements in design and materials can be implemented. The first part of this effort consists of a strain gage alloy development program which will be followed by an investigation of complete strain gage systems. Efforts to date are summarized.

  15. Hydrogen desorption property of mechanically prepared nanostructured graphite

    NASA Astrophysics Data System (ADS)

    Orimo, S.; Matsushima, T.; Fujii, H.; Fukunaga, T.; Majer, G.

    2001-08-01

    Two desorption peaks of hydrogen molecule (mass number=2), starting at about 600 and 950 K, respectively, are observed in thermal desorption mass spectroscopy of nanostructured graphite mechanically milled for 80 h under hydrogen atmosphere. It follows from a combined analysis of thermal desorption mass spectroscopy and thermogravimetry, that 6 mass % of hydrogen (corresponding to 80% of the total amount of hydrogen) is desorbed at the first desorption peak as a mixture of pure hydrogen and hydrocarbons. Below the temperature of the second desorption peak, at which recrystallization related desorption occurs, nanostructured graphite is expected to retain its specific defective structures mainly with carbon dangling bonds as suitable trapping sites for hydrogen storage. The formation process of the nanostructures during milling under hydrogen atmosphere is also discussed on the basis of the profile of Raman spectroscopy.

  16. Thermal reaction and desorption behaviors of 2,5-diiodothiophene on clean and passivated Au surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Guangming; Ryoo, Kunkul; Kim, Seong H.

    2007-07-01

    Thermal reactions and desorption behaviors of 2,5-diiodothiophene on Au were studied with temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Diiodo-substituted hetero-cyclic molecules are an important precursor molecule for photochemical production of conjugated polymers. This paper describes the surface reactions and multilayer structure of 2,5-diiodothiophene in the absence of photon irradiation. 2,5-Diiodothiophene adsorbs molecularly on Au at 100 K. At 200-300 K, the C-I bond of the molecule dissociates producing atomic iodine. The C-I bond cleavage appears to induce further dissociation of the thiophene ring structure. The iodine species desorb at 600-750 K from the surface. The dissociated carbon and sulfur remain on the Au surface even at 800 K. The desorption of thin multilayers occurs at 220 K. During the desorption of these layers, a clustering process seems to occur. The desorption of thick multilayer occurs at 235 K.

  17. Silicone rod extraction followed by liquid desorption-large volume injection-programmable temperature vaporiser-gas chromatography-mass spectrometry for trace analysis of priority organic pollutants in environmental water samples.

    PubMed

    Delgado, Alejandra; Posada-Ureta, Oscar; Olivares, Maitane; Vallejo, Asier; Etxebarria, Nestor

    2013-12-15

    In this study a priority organic pollutants usually found in environmental water samples were considered to accomplish two extraction and analysis approaches. Among those compounds organochlorine compounds, pesticides, phthalates, phenols and residues of pharmaceutical and personal care products were included. The extraction and analysis steps were based on silicone rod extraction (SR) followed by liquid desorption in combination with large volume injection-programmable temperature vaporiser (LVI-PTV) and gas chromatography-mass spectrometry (GC-MS). Variables affecting the analytical response as a function of the programmable temperature vaporiser (PTV) parameters were firstly optimised following an experimental design approach. The SR extraction and desorption conditions were assessed afterwards, including matrix modification, time extraction, and stripping solvent composition. Subsequently, the possibility of performing membrane enclosed sorptive coating extraction (MESCO) as a modified extraction approach was also evaluated. The optimised method showed low method detection limits (3-35 ng L(-1)), acceptable accuracy (78-114%) and precision values (<13%) for most of the studied analytes regardless of the aqueous matrix. Finally, the developed approach was successfully applied to the determination of target analytes in aqueous environmental matrices including estuarine and wastewater samples. PMID:24209370

  18. Summary of Jimsonde temperature profiles. Part 2: Programs, data comments

    NASA Technical Reports Server (NTRS)

    Willett, J. A.

    1981-01-01

    Natural environment criteria are established and interpreted for aeronautical vehicle design and engineering operations. Data summaries, computer formats, frequency distributions, and composite listings of the temperature profiles acquisition program are included.

  19. THERMAL DESORPTION...NOW YOU'RE COOKIN'

    EPA Science Inventory

    Thermal desorption includes a number of ex situ processes that use either direct or indirect heat exchange to heat a waste material to volatilize organic materials. hermal desorption systems typically operate at soil treatment temperatures in the range of 400 to 600 degrees F to ...

  20. Program for an improved hypersonic temperature-sensing probe

    NASA Technical Reports Server (NTRS)

    Reilly, Richard J.

    1993-01-01

    Under a NASA Dryden-sponsored contract in the mid 1960s, temperatures of up to 2200 C were successfully measured using a fluid oscillator. The current program, although limited in scope, explores the problem areas which must be solved if this technique is to be extended to 10,000 R. The potential for measuring extremely high temperatures, using fluid oscillator techniques, stems from the fact that the measuring element is the fluid itself. The containing structure of the oscillator need not be brought to equilibrium temperature with with the fluid for temperature measurement, provided that a suitable calibration can be arranged. This program concentrated on review of high-temperature material developments since the original program was completed. Other areas of limited study included related pressure instrumentation requirements, dissociation, rarefied gas effects, and analysis of sensor time response.

  1. Decomposition of methanol, formaldehyde, and formic acid on nonpolar (1010), stepped (5051), and (0001) surfaces of ZnO by temperature-programmed decomposition

    SciTech Connect

    Akhter, S.; Cheng, W.H.; Lui, K.; Kung, H.H.

    1984-02-01

    The decomposition of methanol, formaldehyde, and formic acid were studied on a nonpolar (1010), a stepped (5051) and a Zn polar (0001) surface by temperature-programmed decomposition. The decomposition products on the (1010) and (5051) surfaces were similar, but the coverage and the amounts of products were consistently higher on the (5051) surface. Two pathways for decomposition of methanol are proposed, dissociatively adsorbed oxygen at 150/sup 0/C and oxidation of methoxide to a surface formate-like species. Formaldehyde and formic acid also decomposed via the surface formate. The competition between dehydrogenation and oxidation depended on the coverage such that dehydrogenation was more favored for higher coverages. Decomposition products were identified for the two pathways for the different compounds. Desorption of all the decomposition products wasreaction-limited except for water which was desorption-limited. The results indicated that the (0001) surface is more metallic in its behavior than the (1010) and (5051) surfaces. Comparison of the desorption temperatures of different compounds suggests that at room temperature, alcohols adsorb molecularly on the (0001) surface but dissociatively on the other two surfaces. On the (0001), comparison among methanol, ethanol, and isopropanol suggests that the ease of dehydrogenation parallels the strength of the ..cap alpha../sub C-H/ bond.

  2. Desorption of water from distinct step types on a curved silver crystal.

    PubMed

    Janlamool, Jakrapan; Bashlakov, Dima; Berg, Otto; Praserthdam, Piyasan; Jongsomjit, Bunjerd; Juurlink, Ludo B F

    2014-01-01

    We have investigated the adsorption of H2O onto the A and B type steps on an Ag single crystal by temperature programmed desorption. For this study, we have used a curved crystal exposing a continuous range of surface structures ranging from [5(111) (100)] via (111) to [5(111) (110)]. LEED and STM studies verify that the curvature of our sample results predominantly from monoatomic steps. The sample thus provides a continuous array of step densities for both step types. Desorption probed by spatially-resolved TPD of multilayers of H2O shows no dependence on the exact substrate structure and thus confirms the absence of thermal gradients during temperature ramps. In the submonolayer regime, we observe a small and linear dependence of the desorption temperature on the A and B step density. We argue that such small differences are only observable by means of a single curved crystal, which thus establishes new experimental benchmarks for theoretical calculation of chemically accurate binding energies. We propose an origin of the observed behavior based on a "two state" desorption model. PMID:25068782

  3. DESORPTION OF SORBATES FROM MST, MMST, AND CST UNDER VARIOUS CONDITIONS

    SciTech Connect

    Taylor-Pashow, K.; Hobbs, D.

    2011-06-10

    The Small Column Ion Exchange (SCIX) Program (formerly referred to as the Modular Salt Processing (MSP) Project) seeks to deploy equipment to remove the {sup 134,137}Cs, {sup 90}Sr, and alpha-emitting radionuclides (principally {sup 238,239,240}Pu and {sup 237}Np) from the high level waste salt solutions. The equipment is installed within a high level waste tank to take advantage of the shielding provided by the waste tank. The process will involve adding monosodium titanate (MST) to the waste tank (i.e., Tank 41H) to sorb the Sr and select actinides, removing the MST and entrained sludge with in-riser rotary microfilters, and subsequently using ion-exchange columns containing crystalline silicotitanate (CST) to remove the Cs. After being loaded with Cs, the CST will be ground to reduce the particle size and then transferred into another waste tank (e.g., Tank 40H). The MST and sludge solids stream will be transported to a sludge batch preparation tank (i.e., Tank 42H or Tank 51H) once the SCIX batch is processed. Both streams, MST/solids and CST, will ultimately be transported into and vitrified inside the Defense Waste Processing Facility (DWPF). A series of experiments were performed to examine desorption from monosodium titanate (MST), modified monosodium titanate (mMST), and crystalline silicotitanate (CST) under various conditions. The first two experiments examined desorption from MST and CST under two different sludge treatment processes, aluminum dissolution and sludge washing. Desorption of all sorbates was observed to varying degrees under the aluminum dissolution conditions. The extent of desorption ranged from < 3% to about 50% after 4 weeks, with Pu exhibiting the lowest desorption. At the end of the experiment, the temperature was reduced from 65 C to 25 C and the tests monitored for an additional two weeks. After reducing the temperature, partial resorption of the sorbates was observed with both MST and CST. Under the sludge washing conditions, no desorption of sorbates was observed with MST; however, some additional sorption did occur. For CST, a small amount of Cs leached from the material during the first day of testing, but no further leaching was observed over the remaining test period. The final test was designed to examine the possibility of desorption from both MST and mMST upon increasing the solid to liquid phase ratio. The results of these tests indicated some desorption of Pu from MST within the first two weeks after changing the phase ratio, then resorption of some of the leached Pu over the remaining 4 weeks of the experiment. No desorption of any sorbates was observed for mMST under these conditions.

  4. FINAL REPORT. HIGH TEMPERATURE CONDENSED PHASE MASS SPECTROMETRIC ANALYSIS PROGRAM

    EPA Science Inventory

    This project was funded by the EM Science Program for the development of an integrated mass spectrometric analysis system capable of analyzing materials from room up to high temperatures, with the practical upper temperature limit to be experimentally determined. A primary object...

  5. THERMAL DESORPTION OF PETROLEUM CONTAMINATED SOILS

    EPA Science Inventory

    The U.S. Environmental Protection Agency recently funded a study which addresses the treatment of soils contaminated by petroleum hydrocarbons using low temperature thermal desorption (LTTD). he proposed paper will summarize some of the results of that study. TTD has become a maj...

  6. COMPOUND IDENTIFICATION IN ORGANIC AEROSOLS USING TEMPERATURE-PROGRAMMED THERMAL DESORPTION PARTICLE BEAM MASS SPECTROMETRY. (R826235)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  7. NASA's high-temperature engine materials program for civil aeronautics

    NASA Technical Reports Server (NTRS)

    Gray, Hugh R.; Ginty, Carol A.

    1992-01-01

    The Advanced High-Temperature Engine Materials Technology Program is described in terms of its research initiatives and its goal of developing propulsion systems for civil aeronautics with low levels of noise, pollution, and fuel consumption. The program emphasizes the analysis and implementation of structural materials such as polymer-matrix composites in fans, casings, and engine-control systems. Also investigated in the program are intermetallic- and metal-matrix composites for uses in compressors and turbine disks as well as ceramic-matrix composites for extremely high-temperature applications such as turbine vanes.

  8. Adsorption and desorption of butanethiol on Au?100?-(520)

    NASA Astrophysics Data System (ADS)

    Bondzie, V.; Dixon-Warren, St. J.; Yu, Y.; Zhang, L.

    1999-07-01

    The adsorption and desorption of butanethiol in ultra-high vacuum on Au{100}-(520) has been investigated using temperature programmed desorption/reaction (TPD/R), low energy electron diffraction and Auger electron spectroscopy. The TPD/R results clearly show that butanethiol adsorbs into both a chemisorbed and a physisorbed state. Desorption of physisorbed butanethiol occurs molecularly at 138 K. By contrast, desorption of the chemisorbed butanethiolate species occurs with decomposition at 500 K to yield primarily 1-butene; the thiol sulfur remains adsorbed on the surface and either desorbs or possibly dissolves into the bulk of the gold sample at above 700 K. The substrate temperature dependence of the chemisorption process suggests a precursor mechanism for the chemisorption kinetics. The TPD/R results also show that chemisorption does not occur on a very clean and ordered Au{100}-(520) surface at 100 K, and that low coverages of pre-adsorbed sulfur atoms facilitate the chemisorption process, suggesting a defect-mediated precursor mechanism.

  9. Overview of NASA's advanced high temperature engine materials technology program

    NASA Technical Reports Server (NTRS)

    Ginty, Carol A.; Gray, Hugh R.

    1992-01-01

    NASA's 'HITEMP' program has been charged with development of propulsion systems technologies for next-generation civil and military aircraft, stressing high-temperature/low-density composites. These encompass polymer-matrix composites for fans, ducts, and compressor cases, and intermetallic and metallic alloy matrix composites for applications in turbine disks, blades, and vanes, and ceramic matrix composites for combustors and turbines. An overview is presented of program concerns and achievements to date.

  10. Correlation between the processes of water desorption and tritium release from Li4SiO4 ceramic pebbles

    NASA Astrophysics Data System (ADS)

    Ran, Guangming; Xiao, Chengjian; Chen, Xiaojun; Gong, Yu; Kang, Chunmei; Wang, Xiaolin

    2015-11-01

    The correlation between water desorption and tritium release from Li4SiO4 pebbles was studied by temperature programmed desorption. The released water and tritium from irradiated samples were monitored simultaneously. The main peak for tritium release from the irradiated samples that were exposed to air for more than a month, was shifted from 500 to about 250 °C, as compared to that from the unexposed samples. The peak temperatures for water desorption and tritium release overlapped very well, suggesting a strong correlation between the two processes. Accordingly, a two-step mechanism, involving isotope exchange between the tritium trapped on the grain surface and the surface hydroxyls (-OH), and subsequent desorption of tritiated water through recombination of the -OH/-OT groups, was proposed to explain the tritium release behavior for the air-exposed samples. It is believed that the formation and desorption of surface hydroxyl groups at 200-300 °C can affect the behavior of tritium release from Li4SiO4 significantly.

  11. Temperature-programmed GC using silicon microfabricated columns with integrated heaters and temperature sensors.

    PubMed

    Reidy, Shaelah; George, Don; Agah, Masoud; Sacks, Richard

    2007-04-01

    Columns were fabricated in silicon substrates by deep reactive-ion etching. The channels were sealed with a glass wafer anodically bonded to the silicon surface. Heaters and temperature sensors were fabricated on the back side of each column chip. A microcontroller-based temperature controller was used with a PC for temperature programming. Temperature programming, with channel lengths of 3.0 and 0.25 m, is described. The 3.0-m-long channel was fabricated on a 3.2 cmx3.2 cm chip. Four columns were fabricated on a standard 4-in. silicon wafer. The 0.25-m-long channel was fabricated on a 1.1 cmx1.1 cm chip, and approximately 40 columns could be fabricated on a 4-in. wafer. All columns were coated with a nonpolar poly(dimethylsiloxanes) stationary phase. A static coating procedure was employed. The 3.0-m-long column generated about 12000 theoretical plates, and the 0.25-m-long channel generated about 1000 plates at optimal carrier gas velocity. Linear temperature ramps as high as 1000 degrees C/min when temperature programmed from 30 to 200 degrees C were obtained with the shorter column. With the 0.25-m-long column, normal alkanes from n-C5 through n-C15 were eluted in less than 12 s using a temperature ramp rate of 1000 degrees C/min. Temperature uniformity over the column chip surface was measured with infrared imaging. A variation of about 2 degrees C was obtained for the 3.0-m-long channel. Retention time reproducibility with temperature programming typically ranged from +/-0.15% to +/-1.5%. Design of the columns and the temperature controller are discussed. Performance data are presented for the different columns lengths. PMID:17311465

  12. The first layer of water on Rh(111): Microscopic structure and desorption kinetics

    SciTech Connect

    Beniya, Atsushi; Yamamoto, Susumu; Mukai, Kozo; Yamashita, Yoshiyuki; Yoshinobu, Jun

    2006-08-07

    The adsorption states and growth process of the first water (D{sub 2}O) layer on Rh(111) were investigated using infrared reflection absorption spectroscopy, temperature programed desorption, and spot-profile-analysis low energy electron diffraction. Water molecules wet the Rh(111) surface intact. At the early stage of first layer growth, a ({radical}3x{radical}3)R30 deg. commensurate water layer grows where 'up' and 'down' species coexist; the up and down species represent water molecules which have free OD, pointing to a vacuum and the substrate, respectively. The up domain was a flatter structure than an icelike bilayer. Water desorption from Rh(111) was a half-order process. The activation energy and the preexponential factor of desorption are estimated to be 60 kJ/mol and 4.8x10{sup 16} ML{sup 1/}2/s at submonolayer coverage, respectively. With an increase in water coverage, the flat up domain becomes a zigzag layer, like an ice bilayer. At the saturation coverage, the amount of down species is 1.3 times larger than that of the up species. In addition, the activation energy and the preexponential factor of desorption decrease to 51 kJ/mol and 1.3x10{sup 14} ML{sup 1/2}/s, respectively.

  13. Isothermal and isobaric desorption of carbon dioxide by purge

    SciTech Connect

    Sircar, S.; Golden, T.C.

    1995-08-01

    Adsorption and desorption constitute the two most basic steps in all pressure swing adsorption (PSA) processes for gas separation. The desorption steps are the primary energy-consuming steps in the PSA process. They also dictate the overall separation efficiency. Isothermal and isobaric desorption of carbon dioxide was experimentally evaluated by purging adsorbent columns saturated with pure carbon dioxide with pure hydrogen, nitrogen, and methane. Three different activated carbons and two zeolites were investigated as adsorbents. The effects of purge gas flow rate, system pressure and temperature, strength of carbon dioxide adsorption, and selectivity of adsorption between carbon dioxide and the purge gas on the desorption process were measured. Instantaneous local equilibrium between gas and adsorbed phases was established under the conditions of the experiments. An analytical mathematical model for isothermal and isobaric desorption of binary gas mixtures by purge was developed. It was demonstrated that the efficiency of desorption by purge can be increased by (1) lowering the desorption pressure, (2) increasing the adsorbent temperature, and (3) increasing the selectivity of adsorption of the purge gas over the desorbing component.

  14. Thermal desorption of metals from tungsten single crystal surfaces

    NASA Technical Reports Server (NTRS)

    Bauer, E.; Bonczek, F.; Poppa, H.; Todd, G.

    1975-01-01

    After a short review of experimental methods used to determine desorption energies and frequencies the assumptions underlying the theoretical analysis of experimental data are discussed. Recent experimental results on the flash desorption of Cu, Ag, and Au from clean, well characterized W (110) and (100) surfaces are presented and analyzed in detail with respect to the coverage dependence. The results obtained clearly reveal the limitations of previous analytical methods and of the experimental technique per se (such as structure and phase changes below and in the temperature region in which desorption occurs).

  15. Relative reactivities of amino and ethenyl groups in allylamine on Si(100)2 × 1: Temperature-dependent X-ray photoemission and thermal desorption studies of a common linker molecule

    NASA Astrophysics Data System (ADS)

    Radi, A.; Ebrahimi, M.; Leung, K. T.

    2010-07-01

    The room-temperature adsorption and thermal evolution of allylamine on Si(100)2 × 1 have been investigated by using temperature-dependent X-ray photoelectron spectroscopy (XPS) and thermal desorption spectrometry (TDS). The presence of a broad N 1 s feature at 398.9 eV, attributed to a N―Si bond, indicates N―H dissociative adsorption. On the other hand, the presence of C 1 s features at 284.6 eV and 286.2 eV, corresponding to C═C and C―N, respectively, and the absence of the Si―C feature expected at 283.2 eV shows that [2 + 2] C═C cycloaddition does not occur at room temperature. These XPS data are consistent with the unidentate staggered and eclipsed allylamine conformer adstructures arising from N―H dissociation and not [2 + 2] C═C cycloaddition. The apparent conversion of the N 1 s feature for Si―N(H)―C ? at 398.9 eV to that for Si―N(H) at 397.7 eV and the total depletion of C 1 s feature for C―N at 286.2 eV near 740 K indicates cleavage of the C―N bond, leaving behind a Si―N(H) rad radical. Furthermore, the C═C C 1 s feature at 284.6 eV undergoes steep intensity reduction between 740 K and 825 K, above which a new C 1 s feature at 283.2 eV corresponding to SiC is found to emerge. These spectral changes suggest total dissociation of the ethenyl fragment and the formation of SiC. Moreover, while the total N 1 s intensity undergoes a minor reduction (24%) upon annealing up to 1090 K, a considerable reduction (43%) is found in the overall C 1 s intensity. This observation is consistent with our TDS data, which shows the desorption of C-containing molecules including propene and ethylene at 580 K and of acetylene at 700 K. The lack of N-containing desorbates suggests that the dissociated N species are likely bonded to multiple surface Si atoms or diffused into the bulk. Interestingly, both the staggered and eclipsed N―H dissociative adstructures are found to have a less negative adsorption energy than the [N, C, C] tridentate or the [2 + 2] C═C cycloaddition adstructures by our DFT calculations, which suggests that the observed formation of N―H dissociative adstructures is kinetically favored on the Si(100)2 × 1 surface.

  16. Activation energies of phenanthrene desorption from carbonaceous materials: Column studies

    NASA Astrophysics Data System (ADS)

    Wang, Guohui; Grathwohl, Peter

    2009-05-01

    SummarySorption/desorption kinetics of phenanthrene from two carbonaceous samples (lignite and high-volatile bituminous coal (HC)) at different temperatures was monitored using an on-line column method. Pulverized samples (<30 ?m) were equilibrated in the column for 2 months before desorption began. The desorption rates declined initially fast, followed by an extended tailing part, which could be described very well by a single parameter spherical diffusion model accounting for non-linear sorption. Desorption was carried out at stepwise increased temperatures (20-90 C), and the apparent activation energies were calculated based on the Arrhenius relationship for each of totally three temperature steps. The apparent activation energies were in an order of 58-66 kJ mol -1 and 70-71 kJ mol -1 for lignite and HC, respectively and they did not increase significantly during the leaching procedure. At the end of the experiments desorption was almost complete and only 0.2% (lignite) and 6% (HC) of the initially sorbed phenanthrene was present after the last temperature step. Fitted diffusion coefficients as well as the comparison between the apparent activation energies and sorption/desorption enthalpies obtained for the same samples from equilibrium isotherms imply that the diffusion occurred in organic matter of the lignite and in micropores of the high-volatile bituminous coal, where higher apparent activation energies are expected.

  17. Programmed temperature vaporizing injector to filter off disturbing high boiling and involatile material for on-line high performance liquid chromatography gas chromatography with on-column transfer.

    PubMed

    Biedermann, Maurus; Grob, Koni

    2013-03-15

    Insertion of a programmed temperature vaporizing (PTV) injector under conditions of concurrent solvent recondensation (CSR) into the on-line HPLC-GC interface for on-column transfer (such as the retention gap technique with partially concurrent eluent evaporation) enables filtering off high boiling or involatile sample constituents by a desorption temperature adjusted to the required cut-off. Details of this technique were investigated and optimized. Memory effects, observed when transferred liquid was sucked backwards between the transfer line and the wall of the injector liner, can be kept low by a small purge flow rate through the transfer line at the end of the transfer and the release of the liquid through a narrow bore capillary kept away from the liner wall. The column entrance should be within the well heated zone of the injector to prevent losses of solute material retained on the liner wall during the splitless period. The desorption temperature must be maintained until an elevated oven temperature is reached to prevent peak broadening resulting of a cool inlet section in the bottom part of the injector. PMID:23394744

  18. Thermal helium desorption behavior in advanced ferritic steels

    NASA Astrophysics Data System (ADS)

    Kimura, Akihiko; Sugano, R.; Matsushita, Y.; Ukai, S.

    2005-02-01

    Thermal helium desorption measurements were performed to investigate the difference in the helium trapping and accumulation behavior among a reduced activation ferritic (RAF) steel and oxide dispersion strengthening (ODS) steels after implantation of He+ ions at room temperature. Thermal helium desorption spectra (THDS) were obtained during annealing to 1200 C at a heating rate of 1 C/s. The THDS of the ODS steels are very similar to that of the RAF steel, except for the presence of the peak in the temperature range from 800 to 1000 C, where the ? ? transformation related helium desorption from the ?-phase is considered to occur in the 9Cr-ODS martensitic steels. The fraction of helium desorption becomes larger at higher temperatures, and this trend is increased with the amount of implanted helium. In the 9Cr-ODS steels, the fraction of helium desorption by bubble migration mechanism was smaller than that in the RAF steel. This suggests that the bubble formation was suppressed in the ODS steels. In the 12Cr-ODS steel, the fraction of helium desorption by bubble migration reached more than 90%, suggesting that the trapping capacity of martensite phase in the 9Cr-ODS steel is rather large.

  19. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  20. High temperature static strain gage alloy development program

    NASA Technical Reports Server (NTRS)

    Hulse, C. O.; Bailey, R. S.; Lemkey, F. D.

    1985-01-01

    The literature, applicable theory and finally an experimental program were used to identify new candidate alloy systems for use as the electrical resistance elements in static strain gages up to 1250K. The program goals were 50 hours of use in the environment of a test stand gas turbine engine with measurement accuracies equal to or better than 10 percent of full scale for strains up to + or - 2000 microstrain. As part of this effort, a computerized electrical resistance measurement system was constructed for use at temperatures between 300K and 1250K and heating and cooling rates of 250K/min and 10K/min. The two best alloys were an iron-chromium-aluminum alloy and a palladium base alloy. Although significant progress was made, it was concluded that a considerable additional effort would be needed to fully optimize and evaluate these candidate systems.

  1. Cooled High-temperature Radial Turbine Program 2

    NASA Technical Reports Server (NTRS)

    Snyder, Philip H.

    1991-01-01

    The objective of this program was the design and fabrication of a air-cooled high-temperature radial turbine (HTRT) intended for experimental evaluation in a warm turbine test facility at the LeRC. The rotor and vane were designed to be tested as a scaled version (rotor diameter of 14.4 inches diameter) of a 8.021 inch diameter rotor designed to be capable of operating with a rotor inlet temperature (RIT) of 2300 F, a nominal mass flow of 4.56 lbm/sec, a work level of equal or greater than 187 Btu/lbm, and efficiency of 86 percent or greater. The rotor was also evaluated to determine it's feasibility to operate at 2500 F RIT. The rotor design conformed to the rotor blade flow path specified by NASA for compatibility with their test equipment. Fabrication was accomplished on three rotors, a bladeless rotor, a solid rotor, and an air-cooled rotor.

  2. Multiyear Program Plan for the High Temperature Materials Laboratory

    SciTech Connect

    Arvid E. Pasto

    2000-03-17

    Recently, the U.S. Department of Energy's (DOE) Office of Heavy Vehicle Technologies (OHVT) prepared a Technology Roadmap describing the challenges facing development of higher fuel efficiency, less polluting sport utility vehicles, vans, and commercial trucks. Based on this roadmap, a multiyear program plan (MYPP) was also developed, in which approaches to solving the numerous challenges are enumerated. Additional planning has been performed by DOE and national laboratory staff, on approaches to solving the numerous challenges faced by heavy vehicle system improvements. Workshops and planning documents have been developed concerning advanced aerodynamics, frictional and other parasitic losses, and thermal management. Similarly, the Heavy Vehicle Propulsion Materials Program has developed its own multiyear program plan. The High Temperature Materials Laboratory, a major user facility sponsored by OHVT, has now developed its program plan, described herein. Information was gathered via participation in the development of OHVT's overall Technology Roadmap and MYPP, through personal contacts within the materials-user community, and from attendance at conferences and expositions. Major materials issues for the heavy vehicle industry currently center on trying to increase efficiency of (diesel) engines while at the same time reducing emissions (particularly NO{sub x} and particulates). These requirements dictate the use of increasingly stronger, higher-temperature capable and more corrosion-resistant materials of construction, as well as advanced catalysts, particulate traps, and other pollution-control devices. Exhaust gas recirculation (EGR) is a technique which will certainly be applied to diesel engines in the near future, and its use represents a formidable challenge, as will be described later. Energy-efficient, low cost materials processing methods and surface treatments to improve wear, fracture, and corrosion resistance are also required.

  3. Desorption Dynamics, Internal Energies and Imaging of Organic Molecules from Surfaces with Laser Desorption and Vacuum Ultraviolet (VUV) Photoionization

    SciTech Connect

    Kostko, Oleg; Takahashi, Lynelle K.; Ahmed, Musahid

    2011-04-05

    There is enormous interest in visualizing the chemical composition of organic material that comprises our world. A convenient method to obtain molecular information with high spatial resolution is imaging mass spectrometry. However, the internal energy deposited within molecules upon transfer to the gas phase from a surface can lead to increased fragmentation and to complications in analysis of mass spectra. Here it is shown that in laser desorption with postionization by tunable vacuum ultraviolet (VUV) radiation, the internal energy gained during laser desorption leads to minimal fragmentation of DNA bases. The internal temperature of laser-desorbed triacontane molecules approaches 670 K, whereas the internal temperature of thymine is 800 K. A synchrotron-based VUV postionization technique for determining translational temperatures reveals that biomolecules have translational temperatures in the range of 216-346 K. The observed low translational temperatures, as well as their decrease with increased desorption laser power is explained by collisional cooling. An example of imaging mass spectrometry on an organic polymer, using laser desorption VUV postionization shows 5 mu m feature details while using a 30 mu m laser spot size and 7 ns duration. Applications of laser desorption postionization to the analysis of cellulose, lignin and humic acids are briefly discussed.

  4. Progress in BNL High-Temperature Hydrogen Combustion Research Program

    SciTech Connect

    Ciccarelli, G.; Ginsberg, T.; Boccio, J.; Curtiss, J.; Economos, C.; Jahelka, J.; Sato, K.

    1992-12-31

    The objectives of the BNL High-Temperature Hydrogen Combustion Research Program are discussed. The experimental facilities are described and two sets of preliminary experiments are presented. Chemical reaction time experiments have been performed to determine the length of time reactive mixtures of interest can be kept at temperature before reaction in the absence of ignition sources consumes the reactants. Preliminary observations are presented for temperatures in the range 588K--700K. Detonation experiments are described in which detonation cell width is measured as a measure of mixture sensitivity to detonation. Preliminary experiments are described which are being carried out to establish data reproducibility with previous measurements in the literature and to test out and refine experimental methods. Intensive studies of hydrogen combustion phenomena were carried out during the 1980s. Much of this effort was driven by issues related to nuclear reactor safety. The ``high-speed`` combustion phenomena of flame acceleration, deflagration-to-detonation transition, direct initiation of detonation, detonation propagation, limits of detonation in tubes and channels, transmission of detonations from confined to unconfined geometry and other related phenomena were studied using a variety of gaseous fuel-oxidant systems, including hydrogen-steam-air systems of interest in reactor safety studies. Several reviews are available which document this work [Lee, 1989; Berman, 1986].

  5. Progress in BNL High-Temperature Hydrogen Combustion Research Program

    SciTech Connect

    Ciccarelli, G.; Ginsberg, T.; Boccio, J.; Curtiss, J.; Economos, C.; Jahelka, J.; Sato, K.

    1992-01-01

    The objectives of the BNL High-Temperature Hydrogen Combustion Research Program are discussed. The experimental facilities are described and two sets of preliminary experiments are presented. Chemical reaction time experiments have been performed to determine the length of time reactive mixtures of interest can be kept at temperature before reaction in the absence of ignition sources consumes the reactants. Preliminary observations are presented for temperatures in the range 588K--700K. Detonation experiments are described in which detonation cell width is measured as a measure of mixture sensitivity to detonation. Preliminary experiments are described which are being carried out to establish data reproducibility with previous measurements in the literature and to test out and refine experimental methods. Intensive studies of hydrogen combustion phenomena were carried out during the 1980s. Much of this effort was driven by issues related to nuclear reactor safety. The high-speed'' combustion phenomena of flame acceleration, deflagration-to-detonation transition, direct initiation of detonation, detonation propagation, limits of detonation in tubes and channels, transmission of detonations from confined to unconfined geometry and other related phenomena were studied using a variety of gaseous fuel-oxidant systems, including hydrogen-steam-air systems of interest in reactor safety studies. Several reviews are available which document this work [Lee, 1989; Berman, 1986].

  6. Desorption of hydrogen trapped in carbon and graphite

    NASA Astrophysics Data System (ADS)

    Atsumi, H.; Takemura, Y.; Miyabe, T.; Konishi, T.; Tanabe, T.; Shikama, T.

    2013-11-01

    Thermal desorption behavior of deuterium (D2) from isotropic graphites and a carbon fiber carbon composite (CFC) charged with D2 gas has been investigated to obtain information concerning hydrogen recycling and tritium inventory in fusion experimental devices as well as a futuristic fusion reactor. After thermal desorption experiments were conducted at temperatures up to 1740 K, a desorption peak at approximately 1600 K (peak 4) was discovered. This is in addition to the previously known peak at approximately 1300 K (peak 3). Peak 3 can be attributed to the release of deuterium controlled by the diffusion process in a graphite filler grain and peak 4 can be attributed to the detrapping of deuterium released from an interstitial cluster loop edge site. Activation energies of peaks 3 and 4 are estimated to be 3.48 and 6.93 eV, respectively. TDS spectra of D2 from graphite and CFCs had previously not been thoroughly investigated. A desorption peak at approximately 1600 K was discovered in the TDS spectra for all samples heated with a linear ramp rate of 0.1 K/s. For an isotropic graphite, ISO-880U, four desorption peaks were recognized in the TDS spectra at approximately 660 K, 900 K, 1300 K, and 1600 K. These peaks were named as peaks 1, 2, 3, and 4 in order of increasing temperature. Major desorption peaks (i.e., peaks 3 and 4) were analyzed and discussed in detail. The temperature of peak 3 was dependent on the size of a graphite filler grain. The desorption process is suggested to be controlled by deuterium diffusion within the filler grain with a strong influence of trapping sites, where the migration takes place as a sequence of detrapping and retrapping. The desorption for peak 4 can be ascribed to the detrapping reaction from an interstitial cluster loop edge site. Activation energies were estimated from the peak shift by varying the heating rate of TDS to be 3.48 and 6.93 eV for peaks 3 and 4, respectively. Theoretical desorption curves for peaks 3 and 4 with the above mentioned activation energies were narrower than those for the experimental desorption curve. The observed peak broadening can be attributed to the effects of grain size and activation energy distributions.

  7. Adsorption and desorption of HCl on ice

    SciTech Connect

    Isakson, M.J.; Sitz, G.O.

    1999-04-01

    It is now generally accepted that chemical reactions occurring on the surface of ice particles in polar stratospheric clouds (PSC`s) play a crucial role in the catalytic cycle of chlorine responsible for the ozone destruction. Pulsed molecular beam and mass spectrometric techniques are used to study the adsorption of hydrogen chloride on thin ice films at temperatures from 100 to 170 K. The adsorption and desorption of HCl from an ice surface is relevant to the polar stratosphere where it is thought that chlorine atoms are liberated from reservoir species such as HCl by heterogeneous reactions occurring on the surface of polar stratospheric clouds. The authors have measured the sticking coefficient for HCl at an incident translational energy of 0.09 eV on thin film ice surfaces using a modified version of the reflectivity technique of King and Wells. By modeling the HCl partial pressure versus time waveforms for surface temperatures of 100--125 K, they obtain a sticking coefficient of 0.91 {+-} 0.06. The model incorporates first-order HCl desorption and a loss term also first order in HCl. Fitted kinetic parameters are E{sub des} = 28 kJ/mol, {nu}{sub des} = 2 {times} 10{sup 14} s{sup {minus}1} for desorption and E{sub loss} = 21 kJ/mol, {nu}{sub loss} = 4 {times} 10{sup 11} s{sup {minus}1} for the loss. The loss may be associated with the onset of water diffusion on the ice surface and subsequent ionization or hydration of the HCl. The measured waveforms are inconsistent with diffusion of HCl into the bulk. The apparent reflectivity decreases substantially in the temperature range of 126 to 140 K. This decrease cannot be attributed to an increase in sticking coefficient, a phase change in the ice, or the formation of the hexahydrate state of HCl.

  8. Desorption of Mercury(II) on Kaolinite in the Presence of Oxalate or Cysteine

    SciTech Connect

    Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

    2011-01-01

    Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio- uptake of Hg in aquatic systems. We studied the desorption of Hg(II) on kaolinite in the presence of oxalate or cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, 7), ligand concentration (0.25, 1.0 mM), and temperature (15, 25, 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH-dependant. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but it appeared to enhance the Hg(II) desorption afterwards. The effect of ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particles and in the solution probably can also affect the Hg(II) desorption.

  9. Modelling of field desorption of monocrystal nanotip

    NASA Astrophysics Data System (ADS)

    Nikiforov, K. A.; Krasnova, A. A.

    2015-11-01

    Mathematical and computer model of field desorption process from metal nanocrystal tip is proposed. The radius of curvature on the top of the emitter is about 50 lattice parameters. The model includes initial calculation of intersection between the crystal lattice and emitter shape for bcc and fcc crystal structures. Arbitrary axisymmetric shapes (figures of rotation) can be used for the emitter model. The algorithm for allocation of atoms being desorbed at given time step is based on an analysis of geometric environment with specified local electric field. Polyhedron nanostructured shape of emitter is obtained as result of evaporation. Computer program realization (Matlab stand alone application) is presented.

  10. HYDROGEN AND ITS DESORPTION IN RHIC.

    SciTech Connect

    HSEUH,H.C.

    2002-11-11

    Hydrogen is the dominating gas specie in room temperature, ultrahigh vacuum systems of particle accelerators and storage rings, such as the Relativistic Heavy Ion Collider (RHIC) at Brookhaven. Rapid pressure increase of a few decades in hydrogen and other residual gases was observed during RHIC's recent high intensity gold and proton runs. The type and magnitude of the pressure increase were analyzed and compared with vacuum conditioning, beam intensity, number of bunches and bunch spacing. Most of these pressure increases were found to be consistent with those induced by beam loss and/or electron stimulated desorption from electron multipacting.

  11. Ion Desorption Stability in Superconducting High Energy Physics Proton Colliders

    SciTech Connect

    Turner, W.C.

    1995-05-29

    In this paper we extend our previous analysis of cold beam tube vacuum in a superconducting proton collider to include ion desorption in addition to thermal desorption and synchrotron radiation induced photodesorption. The new ion desorption terms introduce the possibility of vacuum instability. This is similar to the classical room temperature case but now modified by the inclusion of ion desorption coefficients for cryosorbed (physisorbed) molecules which can greatly exceed the coefficients for tightly bound molecules. The sojourn time concept for physisorbed H{sub 2} is generalized to include photodesorption and ion desorption as well as the usually considered thermal desorption. The ion desorption rate is density dependent and divergent so at the onset of instability the sojourn time goes to zero. Experimental data are used to evaluate the H{sub 2} sojourn time for the conditions of the Large Hadron Collider (LHC) and the situation is found to be stable. The sojourn time is dominated by photodesorption for surface density s(H{sub 2}) less than a monolayer and by thermal deposition for s(H{sub 2}) greater than a monolayer. For a few percent of a monolayer, characteristic of a beam screen, the photodesorption rate exceeds ion desorption rate by more than two orders of magnitude. The photodesorption rate corresponds to a sojourn time of approximately 100 sec. The paper next turns to the evaluation of stability margins and inclusion of gases heavier than H{sub 2} (CO, CO{sub 2} and CH{sub 4}), where ion desorption introduces coupling between molecular species. Stability conditions are worked out for a simple cold beam tube, a cold beam tube pumped from the ends and a cold beam tube with a co-axial perforated beam screen. In each case a simple inequality for stability of a single component is replaced by a determinant that must be greater than zero for a gas mixture. The connection with the general theory of feedback stability is made and it is shown that the gains of the diagonal uncoupled feedback loops are first order in the ion desorption coefficients whereas the gains of the off diagonal coupled feedback loops are second and higher order. For this reason it turns out that in practical cases stability is dominated by the uncoupled diagonal elements and the inverse of the largest first order closed loop gain is a useful estimate of the margin of stability. In contrast to the case of a simple cold beam tube, the stability condition for a beam screen does not contain the desorption coefficient for physisorbed molecules, even when the screen temperature is low enough that there is a finite surface density of them on the screen surface. Consequently there does not appear to be any particular advantage to operating the beam screen at high enough temperature to avoid physisorption. Numerical estimates of ion desorption stability are given for a number of cases relevant to LHC and all of the ones likely to be encountered were found to be stable. The most important case, a I % transparency beam screen at {approx}4.2 K, was found to have a stability safety margin of approximately thirty determined by ion desorption of CO. Ion desorption of H{sub 2} is about a factor of eighty less stringent than CO. For these estimates the beam tube surface was assumed to be solvent cleaned but otherwise untreated, for example by a very high temperature vacuum bakeout or by glow discharge cleaning.

  12. n-Alkanes on MgO(100). I: Coverage-Dependent Desorption Kinetics of n-Butane

    SciTech Connect

    Tait, Steven L.; Dohnalek, Zdenek; Campbell, C T.; Kay, Bruce D.

    2005-04-22

    High quality temperature programmed desorption (TPD) measurements of n-butane from MgO(100) have been made for a large number of initial butane coverages (0-3.70 ML) and a wide range of heating ramp rates (0.3-10 K/s). We present a TPD analysis technique which allows the coverage-dependent desorption energy to be accurately determined by mathematical inversion of a TPD spectrum, assuming only that the prefactor is coverage-independent. A variational method is used to determine the prefactor that minimizes the difference between a set of simulated TPD spectra and corresponding experimental data. The best fit for butane desorption from MgO is obtained with a prefactor of 1015.7?1.6 s-1. The desorption energy is 34.9?3.4 kJ/mol at 0.5 ML coverage, and varies with coverage. Simulations based on these results can accurately reproduce TPD experiments for submonolayer initial coverages over a wide range of heating ramp rates (0.3-10 K/s). Advantages and limitations of this method are discussed.

  13. Kinetic modeling of the adsorption and desorption of CO2 on ?-Fe2O3.

    PubMed

    Breyer, Christine; Reichert, Dirk; Seidel, Juergen; Httl, Regina; Mertens, Florian; Kureti, Sven

    2015-10-28

    The present paper addresses the interaction of CO2 with polycrystalline ?-Fe2O3 revealing considerable catalytic activity in CO oxidation to yield CO2. The mechanism of adsorption and desorption of CO2 was investigated by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS), while the kinetics was examined by temperature-programmed desorption (CO2-TPD). For numeric modeling as well as simulation of the surface coverage, an elementary kinetic mean field model was constructed using Arrhenius-based rate expressions. The kinetic parameters of desorption were taken from fitting calculations (A2 = 3.01 10(5) mol (m(2) s)(-1), E2(0) = 112.8 kJ mol(-1), ?2 = 70.2 kJ mol(-1)), whereas the adsorption was considered to be non-activated and the pre-exponential factor was estimated from kinetic gas theory (A1 = 0.0192 m s(-1), E1 = 0 kJ mol(-1)). For model validation, predicted and experimental CO2-TPD profiles were compared and thermodynamic consistency was evaluated by using differential scanning calorimetry (?adsH(250 C) = -129 kJ mol(-1)) as well as literature data. PMID:26411579

  14. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

    SciTech Connect

    Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek; Kay, Bruce D.

    2014-12-18

    We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of these interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.

  15. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    SciTech Connect

    Masashi Shimada; M. Hara; T. Otsuka; Y. Oya; Y. Hatano

    2014-05-01

    Accurately estimating tritium retention in plasma facing components (PFCs) and minimizing its uncertainty are key safety issues for licensing future fusion power reactors. D-T fusion reactions produce 14.1 MeV neutrons that activate PFCs and create radiation defects throughout the bulk of the material of these components. Recent studies show that tritium migrates and is trapped in bulk (>> 10 µm) tungsten beyond the detection range of nuclear reaction analysis technique [1-2], and thermal desorption spectroscopy (TDS) technique becomes the only established diagnostic that can reveal hydrogen isotope behavior in in bulk (>> 10 µm) tungsten. Radiation damage and its recovery mechanisms in neutron-irradiated tungsten are still poorly understood, and neutron-irradiation data of tungsten is very limited. In this paper, systematic investigations with repeated plasma exposures and thermal desorption are performed to study defect annealing and thermal desorption of deuterium in low dose neutron-irradiated tungsten. Three tungsten samples (99.99 at. % purity from A.L.M.T. Co., Japan) irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to high flux (ion flux of (0.5-1.0)x1022 m-2s-1 and ion fluence of 1x1026 m-2) deuterium plasma at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy (TDS) was performed with a ramp rate of 10 °C/min up to 900 °C, and the samples were annealed at 900 °C for 0.5 hour. These procedures were repeated three (for 100 and 200 °C samples) and four (for 500 °C sample) times to uncover damage recovery mechanisms and its effects on deuterium behavior. The results show that deuterium retention decreases approximately 90, 75, and 66 % for 100, 200, and 500 °C, respectively after each annealing. When subjected to the same TDS recipe, the desorption temperature shifts from 800 °C to 600 °C after 1st annealing for the sample exposed to TPE at 500 °C. Tritium Migration Analysis Program (TMAP) analysis reveals that the detrapping energy decreases from 1.8 eV to 1.4 eV, indicating the changes in trapping mechanisms. This paper also summarizes deuterium behavior studies in HFIR neutron-irradiated tungsten under US-Japan TITAN program.

  16. Adsorption and desorption kinetics of alkanethiols on gold(100) and silver(111)

    NASA Astrophysics Data System (ADS)

    Yu, Yan

    The work reported here is concerned with the adsorption and desorption kinetics of short chain-length alkanethiols and hydrogen sulfide on the Au(100) and Ag(111) substrates. A combination of temperature programmed desorption/reaction (TPD/R), low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and molecular beam (MB) methods were used in a UHV system. This study has given insight in to the kinetic mechanism of thiol self-assembled monolayers (SAMs) formation. Similar adsorption and desorption kinetics were observed for methanethiol, ethanethiol, propanethiol, butanethiol, and pentanethiol on Au(100). The TPD/R results clearly show that these short chain-length alkanethiols adsorbs into both a chemisorbed and a physisorbed state. A detail study was performed for butanethiol on the Au(100) substrate. Desorption of physisorbed butanethiol occurs molecularly at 38 K. By contrast, desorption of the chemisorbed butanethiolate species occurs with decomposition at 500 K to yield primarily 1-butene; the thiol sulfur remained adsorbed on the surface and either desorbed or possibly dissolved into the bulk of the gold sample at above 700 K. The substrate temperature dependence of the chemisorption process suggests a precursor mechanism for the chemisorption kinetics. The TPD results also show that chemisorption does not occur on a very clean and ordered Au(100)-(5x20) surface at 100 K, and that low coverages of pre-adsorbed sulfur atoms facilitate the chemisorption process, suggesting a defect-mediated precursor mechanism. Precursor-mediated adsorption kinetics were observed for the adsorption of H2S on the Au(100)-(5x20) and Ag(111) between 80 and 100 K, while Langmuir adsorption kinetics were observed for the adsorption of H 2S on the sulfide covered Au(100)-(1x1)-SH and Ag(111). The TPD/R of H2S from Au(100)-(1x1)-SH showed additional features at higher temperatures which were associated with the disproportionation of chemisorbed HS(ad). Those features were not observed for H2S from sulfide Ag(111).

  17. Atomic Oxygen Desorption from an Amorphous Silicate Surface

    NASA Astrophysics Data System (ADS)

    He, Jiao; Vidali, Gianfranco

    2014-06-01

    Oxygen is the third most abundant element in space. How oxygen-containing molecules form in space, and whether they form through gas-phase or grain-surface reactions, depends largely on the availability of atomic oxygen in gas-phase versus on surfaces of dust grains. The relative abundance of O in gas-phase versus on grain surfaces is determined by the residence time, or equivalently, desorption energy, of atomic oxygen on grain surfaces. Though important in astrochemical modeling, experimental investigations of atomic oxygen desorption from grain surfaces are lacking in the literature. In most astrochemical models, the O desorption energy value has been taken to be 800 K, which is a guessed value without experimental support. Based on this value, the predicted molecular oxygen abundance in space is at least 2 orders of magnitude higher than what space observations have found. This long running discrepancy of molecular oxygen abundance could be resolved if the O desorption energy is twice as the widely used value (Melnick, G., Tolls, V., et al. 2012, Astrophys. J., 752, 26). We performed TPD (thermal programmed desorption) experiments to study the ozone formation process via O+O2 on an amorphous silicate surface that emulates interstellar conditions. A rate equation model was used to characterize the surface kinetics of both atomic and molecular oxygen. The O desorption energy was extracted from rate equation simulations that best fit the TPD data. The value was found to be 1764232 K, which agrees with what Melnick et al. proposed. We suggest that the newly found value for the O desorption energy should be used in astrochemical modeling. This work is supported by NSF, Astronomy & Astrophysics Division (Grants No. 0908108 and 1311958), and NASA (Grant No. NNX12AF38G). We thank Dr. J.Brucato of the Astrophysical Observatory of Arcetri for providing the samples used in these experiments.

  18. Moisture diffusivity in rice components during absorption and desorption

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Moisture diffusivity values of different rice kernel components namely, endosperm, bran and husks are required to solve mathematical models describing absorption and desorption processes. In addition to the rice variety and temperature, the moisture diffusivity also depends on its instantaneous mois...

  19. Method of enhancing selective isotope desorption from metals

    DOEpatents

    Knize, Randall J. (Plainsboro, NJ); Cecchi, Joseph L. (Lawrenceville, NJ)

    1984-01-01

    A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

  20. Dynamics of NF 3 in a condensed film on Au(1 1 1) as studied by electron-stimulated desorption

    NASA Astrophysics Data System (ADS)

    Rze?nicka, Izabela I.; Lee, Junseok; Yates, John T.

    2006-10-01

    We report a low-temperature dynamics study of condensed layers of NF 3 on Au(1 1 1) by time-of-flight electron-stimulated desorption ion angular distribution (TOF-ESDIAD), temperature-programmed desorption (TPD) and low-temperature scanning tunneling microscopy (LT-STM). Upon adsorption at 30 K, molecular NF 3 adsorption occurs first at the step edges and at minor terrace defect sites with the formation of 2D islands. Within the islands, NF 3 is adsorbed in an upright conformation via the nitrogen lone pair electrons projecting fluorine atoms away from the surface as judged by the presence of only a sharp F + central beam in the ESDIAD pattern. At higher coverages, 3D islands start to populate the surface. Electron bombardment of a thick NF 3 (6 ML) layer adsorbed on the Au(1 1 1) surface leads to emission of F +, N +, NF +, NF2+ and NF3+ ions as observed in the TOF-ESD distribution. Upon heating to 37 K, a sudden decrease of the NF2+ and NF3+ ion yield, which is not related to thermal desorption, is observed which reflects the surface migration of NF 3 molecules, leading to local thinning of the film. The thinning process occurs at the temperature of onset of molecular rotations and self-diffusion in the bulk NF 3 crystal. In this process, some NF 3 molecules move closer to the surface which results in higher efficiency for ion neutralization by the underlying metal surface. In the TPD spectra, the monolayer desorption is observed to begin at 65 K, exhibiting zero-order kinetics with an activation energy of 21 kJ/mol.

  1. Erbium hydride thermal desorption : controlling kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2007-08-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report show that hydride film processing parameters directly impact thermal stability. Issues to be addressed include desorption kinetics for dihydrides and trihydrides, and the effect of film growth parameters, loading parameters, and substrate selection on desorption kinetics.

  2. Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

    NASA Astrophysics Data System (ADS)

    Guterl, Jerome; Smirnov, R. D.; Krasheninnikov, S. I.

    2015-07-01

    Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samples exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.

  3. Hydrogen retention in tungsten materials studied by Laser Induced Desorption

    NASA Astrophysics Data System (ADS)

    Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Reinhart, M.; Mller, S.; Sergienko, G.; Samm, U.; 't Hoen, M. H. J.; Manhard, A.; Schmid, K.; Textor Team

    2013-07-01

    Development of methods to characterise the first wall in ITER and future fusion devices without removal of wall tiles is important to support safety assessments for tritium retention and dust production and to understand plasma wall processes in general. Laser based techniques are presently under investigation to provide these requirements, among which Laser Induced Desorption Spectroscopy (LIDS) is proposed to measure the deuterium and tritium load of the plasma facing surfaces by thermal desorption and spectroscopic detection of the desorbed fuel in the edge of the fusion plasma. The method relies on its capability to desorb the hydrogen isotopes in a laser heated spot. The application of LID on bulk tungsten targets exposed to a wide range of deuterium fluxes, fluences and impact energies under different surface temperatures is investigated in this paper. The results are compared with Thermal Desorption Spectrometry (TDS), Nuclear Reaction Analysis (NRA) and a diffusion model.

  4. Candida guilliermondii and other species of candida misidentified as Candida famata: assessment by vitek 2, DNA sequencing analysis, and matrix-assisted laser desorption ionization-time of flight mass spectrometry in two global antifungal surveillance programs.

    PubMed

    Castanheira, Mariana; Woosley, Leah N; Diekema, Daniel J; Jones, Ronald N; Pfaller, Michael A

    2013-01-01

    Candida famata (teleomorph Debaryomyces hansenii) has been described as a medically relevant yeast, and this species has been included in many commercial identification systems that are currently used in clinical laboratories. Among 53 strains collected during the SENTRY and ARTEMIS surveillance programs and previously identified as C. famata (includes all submitted strains with this identification) by a variety of commercial methods (Vitek, MicroScan, API, and AuxaColor), DNA sequencing methods demonstrated that 19 strains were C. guilliermondii, 14 were C. parapsilosis, 5 were C. lusitaniae, 4 were C. albicans, and 3 were C. tropicalis, and five isolates belonged to other Candida species (two C. fermentati and one each C. intermedia, C. pelliculosa, and Pichia fabianni). Additionally, three misidentified C. famata strains were correctly identified as Kodomaea ohmeri, Debaryomyces nepalensis, and Debaryomyces fabryi using intergenic transcribed spacer (ITS) and/or intergenic spacer (IGS) sequencing. The Vitek 2 system identified three isolates with high confidence to be C. famata and another 15 with low confidence between C. famata and C. guilliermondii or C. parapsilosis, displaying only 56.6% agreement with DNA sequencing results. Matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) results displayed 81.1% agreement with DNA sequencing. One strain each of C. metapsilosis, C. fermentati, and C. intermedia demonstrated a low score for identification (<2.0) in the MALDI Biotyper. K. ohmeri, D. nepalensis, and D. fabryi identified by DNA sequencing in this study were not in the current database for the MALDI Biotyper. These results suggest that the occurrence of C. famata in fungal infections is much lower than previously appreciated and that commercial systems do not produce accurate identifications except for the newly introduced MALDI-TOF instruments. PMID:23100350

  5. Infrared Laser Desorption: Mechanisms and Applications

    NASA Astrophysics Data System (ADS)

    Maechling, Claude Ricketts

    1995-01-01

    This thesis describes the use of two-step laser mass spectrometry (L^2MS), a combination of infrared (IR) laser desorption with resonance-enhanced multiphoton ionization (REMPI) and time-of-flight (TOF) mass spectrometry, to investigate (1) the mechanism of IR laser desorption, (2) the composition of aromatic molecules in extraterrestrial samples, and (3) the measurement of compound-specific carbon isotope ratios. First, a description of the mechanism of IR laser desorption of monolayer and submonolayer coverages of molecules adsorbed to an insulator surface is presented. The vibrational and translational energy distributions of aniline-d7 molecules desorbed from single-crystal sapphire (Al_2 O_3) are recorded using L ^2MS. The energy distributions are found to be in equilibrium with each other and with the temperature of the surface at the time of desorption. The translational and angular distributions of monolayer coverages are altered by the collisions of desorbing molecules with each other. Second, spatial and chemical analyses of the carbonaceous components in chondritic meteorites are presented. A microprobe L^2MS instrument (mu L^2MS) capable of analyzing samples with a spatial resolution of 40 mu m and zeptomole (10^{-21} mole) sensitivity is described and used to investigate polycyclic aromatic hydrocarbons (PAHs) in small particles and heterogeneous samples. PAH distributions are used to distinguish between samples from different meteorite classes, and the effects of thermal processing within a given meteorite class are observed. Sliced wafers of meteorite are found to contain an inhomogeneous distribution of PAHs. muL^2MS studies of meteorite samples are coordinated with scanning electron microscopy studies, and the abundances of aromatic compounds across the surface of a sample are consistent with gross structural features but not with elemental or mineralogical features. Third, a description of a method for performing compound-specific carbon isotope ratio analyses using REMPI followed by TOF mass spectrometry is presented. Measurements of carbon isotope ratios (delta^{13 }C) for the volatile aromatic compounds m-xylene -d10, toluene, and toluene-d8 are described. A simple procedure for deriving the abundances of ^{12 }C and 13C from the TOF spectra is presented, and delta 13C values with a precision of +/-30 parts per million are achieved. Complications caused by and corrections for detector nonlinearity and parent ion fragmentation are discussed.

  6. Space exploration with a solar sail coated by materials that undergo thermal desorption

    NASA Astrophysics Data System (ADS)

    Kezerashvili, Roman Ya.

    2015-12-01

    For extrasolar space exploration it is suggested to use space environmental effects such as solar radiation heating to accelerate a solar sail coated by materials that undergo thermal desorption at a particular temperature. The developed approach allows the perihelion of the solar sail orbits to be determined based on the temperature requirement for the solar sail materials. Our study shows that the temperature of a solar sail increases as r - 2 / 5 when the heliocentric distance r decreases. The proposed sail has two coats of the materials that undergo desorption at different solar sail temperatures depending on the heliocentric distance. The first desorption occurs at the Earth orbit and provides the thrust needed to propel the solar sail toward the Sun. When the solar sail approaches the Sun, its temperature increases, and the second coat undergoes desorption at the perihelion of the heliocentric escape orbit. This provides a second thrust and boosts the solar sail to its escape velocity.

  7. Low-Temperature Geothermal Resources, Geothermal Technologies Program (GTP) (Fact Sheet)

    SciTech Connect

    Not Available

    2010-05-01

    This document highlights the applications of low-temperature geothermal resources and the potential for future uses as well as current Geothermal Technologies Program-funded projects related to low-temperature resources.

  8. Evidence for non-thermalized vibrationally excited molecule production during azomethane pyrolysis in methane desorption from Cu(001)

    NASA Astrophysics Data System (ADS)

    Lallo, J.; Lee, E. V.; Lefkowitz, R.; Hinch, B. J.

    2012-02-01

    A Cu(001) surface was exposed to products of an azomethane pyrolysis doser at varying temperatures. In addition to methyl radical adsorption, for certain doser conditions one or more doser emergent species can undergo an activated adsorption on the copper face. Directly after exposures, temperature programmed desorption between 170 K and 500 K was used to indicate the relative concentrations of adsorbed atomic hydrogen and methyl species, and thermally induced surface reactions. Two methane desorption features were invariably observed, indicating the presence of adsorbed methyl groups (CH3) and transient adsorbed atomic hydrogen. The deduced relative surface concentrations levels of both H and CH3 depend on the total exposures and the operating temperatures of the azomethane pyrolysis doser. The initial H concentrations apparent at surface temperatures between 275 K and 375 K are shown to arise from defect-related methyl decomposition and, at high operating doser temperatures, from the initial adsorption of one or more activated Cu incident species. It is proposed that the distributions of vibrational energies of emergent molecular hydrogen or methane species from higher temperature dosers are non-thermal. Hence, with doser temperatures of 800 °C or above, the effects of subsequent dissociative molecular adsorption on the copper surface can dominate over Cu defect chemistries.

  9. Changes induced on the surfaces of small Pd clusters by the thermal desorption of CO

    NASA Technical Reports Server (NTRS)

    Doering, D. L.; Poppa, H.; Dickinson, J. T.

    1980-01-01

    The stability and adsorption/desorption properties of supported Pd crystallites less than 5 nm in size were studied by Auger electron spectroscopy and repeated flash thermal desorption of CO. The Pd particles were grown epitaxially on heat-treated, UHV-cleaved mica at a substrate temperature of 300 C and a Pd impingement flux of 10 to the 13th atoms/sq cm s. Auger analysis allowed in situ measurement of relative particle dispersion and contamination, while FTD monitored the CO desorption properties. The results show that significant changes in the adsorption properties can be detected. Changes in the Pd Auger signal and the desorption spectrum during the first few thermal cycles are due to particle coalescence and facetting and the rate of this change is dependent on the temperature and duration of the desorption. Significant reductions in the amplitude of the desorptions peak occur during successive CO desorptions which are attributed to increases of surface carbon, induced by the desorption of CO. The contamination process could be reversed by heat treatment in oxygen or hydrogen

  10. Desorption of pyrethroids from suspended solids.

    PubMed

    Fojut, Tessa L; Young, Thomas M

    2011-08-01

    Pyrethroid insecticides have been widely detected in sediments at concentrations that can cause toxicity to aquatic organisms. Desorption rates play an important role in determining the bioavailability of hydrophobic organic compounds, such as pyrethroids, because these compounds are more likely to be sorbed to solids in the environment, and times to reach sorptive equilibrium can be long. In the present study, sequential Tenax desorption experiments were performed with three sorbents, three aging times, and four pyrethroids. A biphasic rate model was fit to the desorption data with r(2) ?>?0.99, and the rapid and slow compartment desorption rate constants and compartment fractions are reported. Suspended solids from irrigation runoff water collected from a field that had been sprayed with permethrin 1 d before were used in the experiments to compare desorption rates for field-applied pyrethroids with those for laboratory-spiked materials. Suspended solids were used in desorption experiments because suspended solids can be a key source of hydrophobic compounds in surface waters. The rapid desorption rate parameters of field-applied permethrin were not statistically different from those of laboratory spiked permethrin, indicating that desorption of the spiked pyrethroids is comparable to desorption of the pyrethroids added and aged in the field. Sorbent characteristics had the greatest effect on desorption rate parameters; as organic carbon content of the solids increased, the rapid desorption fractions and rapid desorption rate constants both decreased. The desorption rate constant of the slow compartment for sediment containing permethrin aged for 28 d was significantly different compared to aging for 1 d and 7 d, whereas desorption in the rapid and slow compartments did not differ between these treatments. PMID:21538493

  11. [Desorption behaviors of 4-nitrophenol on hyper-cross-linked polymer resin NDA-701].

    PubMed

    Hong, Chang-hong; Huang, Ben-sheng; Qiu, Jing; Zhang, Wei-ming

    2011-05-01

    Desorption behaviors of loaded 4-nitrophenol (4-NP) on hyper-cross-linked polymer resin NDA-701 were studied. The molar ratio of NaOH and 4-NP desorbed (M(NAOH/4-NP)) selection experiments were carried out at two different reaction temperature(303 K and 333 K). Desorption kinetics characteristic of4-NP on NDA-701 in the batch and fixed-bed mode were examined at different reaction temperature and M(NaOH/4-NP) values. The results showed that optimal M(NaOH/4-NP) values were 1.2 and 100% 4-NP could be desorbed from NDA-701 at two different temperature. When the M(NaOH/4-NP) was lower than 1.2, the desorption efficiency increases with the increase of temperature, but the function of temperature decrease with increasing of M(NaH/4-NP) values for desorption ratio. The information indicated that desorption thermodynamic characteristic of NDA-701 was controlled by M(NaOH/4-NP) values. Desorption kinetics in the alkaline system can be well described by pseudo-second-order kinetic model, and desorption rate is increased with the increase of desorption temperatures, the k2 value increase from 0.010 g x (mmol x min)(-1) to 0.035 g x (mmol x min)(-1) when desorption temperature increase from 303 K to 333 K. Nevertheless, higher M(NaOH/4-NP) values could not promote desorption rate if only M(NaOH/4-NP) value was larger than the optimal molar ratio of NaOH and 4-NP. When M(NaOH/4-NP) values increase from 1.2 to 5.0, the k2 value increase from 0.038 g x (mmol x min)(-1) to 0.044 g x (mmol x min)(-1) merely at 333 K. the results indicated that desorption kinetic characteristic of NDA-701 was controlled by temperature. NDA-701 can be completely recovered using 2 times Bed Volume of 2% NaOH solution at the temperature of 333 K, comparing with field application, implying that more energy and cost can be saved in comparison with the actual desorption process in the industry. PMID:21780596

  12. Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

    NASA Astrophysics Data System (ADS)

    Danilchenko, B. A.; Yaskovets, I. I.; Uvarova, I. Y.; Dolbin, A. V.; Esel'son, V. B.; Basnukaeva, R. M.; Vinnikov, N. A.

    2014-04-01

    The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or ?-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10-300 K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent with theoretical prediction.

  13. Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

    SciTech Connect

    Danilchenko, B. A. Yaskovets, I. I.; Uvarova, I. Y.; Dolbin, A. V.; Esel'son, V. B.; Basnukaeva, R. M.; Vinnikov, N. A.

    2014-04-28

    The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or ?-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10300?K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent with theoretical prediction.

  14. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

    SciTech Connect

    Smith, R. Scott; Li, Zhenjun; Chen, Long; Dohnalek, Zdenek; Kay, Bruce D.

    2014-07-17

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.

  15. DEUTERIUM, TRITIUM, AND HELIUM DESORPTION FROM AGED TITANIUM TRITIDES. PART I.

    SciTech Connect

    Shanahan, K; Jeffrey Holder, J

    2006-07-10

    Six new samples of tritium-aged bulk titanium have been examined by thermal desorption and isotope exchange chemistry. The discovery of a lower temperature hydrogen desorption state in these materials, previously reported, has been confirmed in one of the new samples. The helium release of the samples shows the more severe effects obtained from longer aging periods, i.e. higher initial He/M ratios. Several of the more aged samples were spontaneously releasing helium. Part I will discuss the new results on the new lower temperature hydrogen desorption state found in one more extensively studied sample. Part II will discuss the hydrogen/helium release behavior of the remaining samples.

  16. Thermal desorption study of potassium from K/deuterated Si(100)2 1

    NASA Astrophysics Data System (ADS)

    Hongo, S.; Taniguchi, S.; Fujimoto, N.; Urano, T.

    1997-04-01

    The shift of the low temperature portion of the potassium desorption spectrum for the K/D/Si(100)2 1 caused by the deuterium preadsorption was discussed by thermal desorption spectroscopy (TDS) and metastable deexcitation spectroscopy (MDS) data. When the Si?D bonds are formed around the K atom, the K(4s) electrons are localized at the K atom. This localization leads to the reduction in the long range dipolar interaction. This explanation is the most plausible for the shift of the low temperature portion of the potassium desorption spectrum.

  17. Moisture desorption isotherms of medium-grain rough rice.

    PubMed

    Basunia, M A.; Abe, T

    2001-07-01

    Moisture desorption isotherms (EMC/ERH) of medium-grain rough rice (Japonica variety) were determined using a constant environment chamber for various combinations of air temperature (11.8-51.0 degrees C) and relative humidity (37.1-89.7%). The initial moisture contents were in the range of 24.7-41.6% dry basis. A thin-layer technique was used to achieve uniform drying. Each test was continued until the moisture content change in 24h was less than 0.1% dry basis. The final moisture content was considered as the dynamic equilibrium moisture content. Four three-parameter EMC/ERH equations, the modified Henderson, modified Chung-Pfost, modified Oswin and modified Halsey equations, were compared for their ability to fit the experimental EMC/ERH data. The residual sum of squares (RSS) and standard error of estimate (SEE) were adopted as the criteria to evaluate the fitting performance of the models. The modified Chung-Pfost equation was identified as the most appropriate equation for representing the EMC/ERH desorption isotherms of rough rice. Coefficients for equilibrium moisture content as a function of equilibrium relative humidity and temperature are given. The EMC/ERH data obtained in this study agreed well with previously published data. However the average isotherm, combining desorption and adsorption data, of ASAE does not predict the desorption EMC of rough rice accurately. PMID:11172858

  18. A soil-column gas chromatography (SCGC) approach to explore the thermal desorption behavior of hydrocarbons from soils.

    PubMed

    Yu, Ying; Liu, Liang; Shao, Ziying; Ju, Tianyu; Sun, Bing; Benadda, Belkacem

    2016-01-01

    A soil-column gas chromatography approach was developed to simulate the mass transfer process of hydrocarbons between gas and soil during thermally enhanced soil vapor extraction (T-SVE). Four kinds of hydrocarbons-methylbenzene, n-hexane, n-decane, and n-tetradecane-were flowed by nitrogen gas. The retention factor k' and the tailing factor T f were calculated to reflect the desorption velocities of fast and slow desorption fractions, respectively. The results clearly indicated two different mechanisms on the thermal desorption behaviors of fast and slow desorption fractions. The desorption velocity of fast desorption fraction was an exponential function of the reciprocal of soil absolute temperature and inversely correlated with hydrocarbon's boiling point, whereas the desorption velocity of slow desorption fraction was an inverse proportional function of soil absolute temperature, and inversely proportional to the log K OW value of the hydrocarbons. The higher activation energy of adsorption was found on loamy soil with higher organic content. The increase of carrier gas flow rate led to a reduction in the apparent activation energy of adsorption of slow desorption fraction, and thus desorption efficiency was significantly enhanced. The obtained results are of practical interest for the design of high-efficiency T-SVE system and may be used to predict the remediation time. PMID:26335523

  19. Desorption of phenol from activated carbon by hot water regeneration. Desorption isotherms

    SciTech Connect

    Bercic, G.; Pintar, A.; Levec, J.

    1996-12-01

    Adsorption of phenol from aqueous solutions at high temperatures on activated carbon was studied. The adsorption capacities were determined by the semicontinuous desorption experiments carried out in a fixed bed adsorber, which was operated in liquid-full mode at a pressure of 25 bar and at temperatures up to 190 C. It was found that in the range of phenol concentrations from 0.005 to 30 g/L the five-parameter Redlich-Petersen adsorption model is equivalent to the six-parameter Fritz-Schluender adsorption model when describing liquid-solid adsorption on the Filtrasorb (F-400) activated carbon. By hot water regeneration, 95% recovery of initial adsorption capacity of activated carbon was obtained. It is also demonstrated that the proposed experimental method for determination of adsorption capacities at high temperatures can be used as an alternative to the traditional method by taking breakthrough curves.

  20. [Thermal desorption behavior of PCDD/Fs on the fly ash].

    PubMed

    Zhang, Feng; Zhang, Hai-jun; Chen, Ji-ping; Liang, Xin-miao

    2008-02-01

    The article studied the thermal desorption behavior of PCDD/Fs on the fly ash under anoxic conditions. From the analysis of the PCDD/Fs concentrations in the gas phrase and solid residual, the several kinds of potential chemical reaction and physical changes of dioxin that occur at the different temperature are concluded. At the same time, desorption ratios of 17 toxic dioxin congers and the better desorption conditions are studied. At 200 degrees C and 300 degrees C, the average desorption ratio of PCDD/Fs are 96.2% and 95.5% respectively. At 400 degrees C, the average desorption ratio of PCDD/Fs is 99.7%. The experiment results show that the PCDD/Fs is dechlorinated at 300 degrees C. At 400 degrees C, a lot of precursor reactions happen in the fly ash, which enhance the content of PCDD/Fs. PMID:18613531

  1. A study of the kinetics of isothermal nicotine desorption from silicon dioxide

    NASA Astrophysics Data System (ADS)

    Adnadjevic, Borivoj; Lazarevic, Natasa; Jovanovic, Jelena

    2010-12-01

    The isothermal kinetics of nicotine desorption from silicon dioxide (SiO 2) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters ( Ea, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the "model-fitting" method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, Ea,α and ln Aα, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.

  2. Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

    SciTech Connect

    Matsuyama, M.; Kondo, M.; Noda, N.; Tanaka, M.; Nishimura, K.

    2015-03-15

    In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

  3. High-temperature oxidation and corrosion of materials program

    SciTech Connect

    Whittle, D.P.

    1980-03-01

    Research progress is reported in the behavior of metals and alloys in gas mixtures at high temperature, corrosion mechanisms in complex environments of low oxidizing potential, hot corrosion of nickel-base alloys at intermediate temperatures, corrosion of solid sulfate deposits, adherence of Al/sub 2/O/sub 3/ oxide films, oxidation behavior of a two-phase alloy Fe-44% Cu, and formation of subscales of varying composition. (FS)

  4. Oregon Low-Temperature-Resource Assessment Program. Final technical report

    SciTech Connect

    Priest, G.R.; Black, G.L.; Woller, N.M.

    1981-01-01

    Numerous low-temperature hydrothermal systems are available for exploitation throughout the Cascades and eastern Oregon. All of these areas have heat flow significantly higher than crustal averages and many thermal aquifers. In northeastern Oregon, low temperature geothermal resources are controlled by regional stratigraphic aquifers of the Columbia River Basalt Group at shallow depths and possibly by faults at greater depths. In southeastern Oregon most hydrothermal systems are of higher temperature than those of northeastern Oregon and are controlled by high-angle fault zones and layered volcanic aquifers. The Cascades have very high heat flow but few large population centers. Direct use potential in the Cascades is therefore limited, except possibly in the cities of Oakridge and Ashland, where load may be great enough to stimulate development. Absence of large population centers also inhibits initial low temperature geothermal development in eastern Oregon. It may be that uses for the abundant low temperature geothermal resources of the state will have to be found which do not require large nearby population centers. One promising use is generation of electricity from freon-based biphase electrical generators. These generators will be installed on wells at Vale and Lakeview in the summer of 1982 to evaluate their potential use on geothermal waters with temperatures as low as 80/sup 0/C (176/sup 0/F).

  5. A Non-linear Temperature-Time Program for Non-isothermal Kinetic Measurements

    NASA Astrophysics Data System (ADS)

    Sohn, Hong Yong

    2016-04-01

    A new temperature-time program for non-isothermal measurements of chemical reaction rates has been developed. The major advantages of the proposed temperature-time function are twofold: Firstly, the analysis of kinetic information in the high temperature range of the measurement is improved over the conventional linear temperature program by slowing the rate of temperature increase in the high temperature range and secondly, the new temperature program greatly facilitates the data analysis by providing a closed-form solution of the temperature integral and allows a convenient way to obtain the kinetic parameters by eliminating the need for the approximate evaluation of the temperature integral. The procedures for applying the new temperature-time program to the analysis of experimental data are demonstrated in terms of the determination of the kinetic parameters based on the selection of a suitable conversion function in the rate equation as well as the direct determination of activation energy at different conversion extents without the need for a conversion function. The rate analysis based on the new temperature program is robust and does not appear to be sensitive to errors in experimental measurements.

  6. A Non-linear Temperature-Time Program for Non-isothermal Kinetic Measurements

    NASA Astrophysics Data System (ADS)

    Sohn, Hong Yong

    2015-12-01

    A new temperature-time program for non-isothermal measurements of chemical reaction rates has been developed. The major advantages of the proposed temperature-time function are twofold: Firstly, the analysis of kinetic information in the high temperature range of the measurement is improved over the conventional linear temperature program by slowing the rate of temperature increase in the high temperature range and secondly, the new temperature program greatly facilitates the data analysis by providing a closed-form solution of the temperature integral and allows a convenient way to obtain the kinetic parameters by eliminating the need for the approximate evaluation of the temperature integral. The procedures for applying the new temperature-time program to the analysis of experimental data are demonstrated in terms of the determination of the kinetic parameters based on the selection of a suitable conversion function in the rate equation as well as the direct determination of activation energy at different conversion extents without the need for a conversion function. The rate analysis based on the new temperature program is robust and does not appear to be sensitive to errors in experimental measurements.

  7. Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite

    SciTech Connect

    Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

    2010-01-01

    Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio-uptake of Hg in the environment. We studied the kinetics of the desorption of Hg(II) from kaolinite as affected by oxalate and cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, and 7), ligand concentration (0.25 and 1.0 mM), and temperature (15 C, 25 C, and 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH dependent. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but the inhibition of the desorption appeared to be less prominent afterwards. The effect of the ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the Hg(II) desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particle surfaces and in the solution phase probably can also affect the Hg(II) desorption.

  8. A Spreadsheet Program for Steady-State Temperature Distributions

    SciTech Connect

    Hutchens, G.J.

    2000-11-01

    A desktop program is developed in Microsoft EXCEL using Visual Basic for Applications (VBA) to solve a two-dimensional steady state heat conduction problem with a radiation boundary condition. The resulting partial differential equation and boundary conditions are solved using finite difference techniques and the results are compared with a finite element solution using the commercially available software package MSC/THERMAL. The results from the two methods are found to be within 1 percent. The VBA solution demonstrates how spreadsheet programs, like EXCEL, can be used to solve practical engineering problems with good accuracy.

  9. High Temperature Materials Needs in NASA's Advanced Space Propulsion Programs

    NASA Technical Reports Server (NTRS)

    Eckel, Andrew J.; Glass, David E.

    2005-01-01

    In recent years, NASA has embarked on several new and exciting efforts in the exploration and use of space. The successful accomplishment of many planned missions and projects is dependent upon the development and deployment of previously unproven propulsion systems. Key to many of the propulsion systems is the use of emergent materials systems, particularly high temperature structural composites. A review of the general missions and benefits of utilizing high temperature materials will be presented. The design parameters and operating conditions will be presented for both specific missions/vehicles and classes of components. Key technical challenges and opportunities are identified along with suggested paths for addressing them.

  10. Chemical desorption and diffusive dust chemistry

    NASA Astrophysics Data System (ADS)

    Dulieu, Francois; Pirronello, Valerio; Minissale, Marco; Congiu, Emanuele; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Accolla, Mario; Cazaux, Stephanie; Manic, Giulio

    In molecular clouds, gaseous species can accrete efficiently on the cold surfaces of dust grains. As for radical-radical reactions, the surface of the grains acts as a third body, and changes dramatically the efficiency of the reactions (i.e., H2 formation), or lowers considerably the barrier to formation (i.e., H2O synthesis) in comparison with gas phase reaction processes. These properties make dust grains efficient catalytic templates. However, the chemical role of dust grains depends on the diffusive properties of the reactive partners. Over the last years, we have developed experimental tools and methods to explore the chemistry occurring on cold (6-50K) surfaces. We have obtained some hints about the diffusivity of H on amorphous ice, and studied in detail the diffusion of O atoms. The latter species appears to have a hopping rate in the range 0.01-100 hops/sec. The diffusion rate of O atoms is dependent on the surface morphology and on the surface temperature. The diffusion law is compatible with a diffusion dominated by quantum tunnelling rather than classical thermal hopping. Using H, O, N atoms and, indirectly, OH and HCO radicals, we have begun to explore many chemical reactive networks. In this presentation, I will focus on the formation of H2O and CO2, and will propose many possible formation routes to obtain these chemical traps. The molecules formed on surfaces have a certain probability of desorbing upon their formation. This non-thermal desorption mechanism, or chemical desorption, has been proposed to explain why some molecules can be detected in the gas phase of those region where they were believed to be part of the icy mantles covering dust grains. We have shown that this process can be very efficient, but is very sensitive to the substrate and the surroundings of the reaction site, is dependent on the kind of molecule formed and its chemical pathway. In my presentation I will present how the surface coverage and the type of reaction can play a major role in the chemical desorption process. I will discuss of possible key parameters that rule this process.

  11. Organic solvent desorption from two tegafur polymorphs.

    PubMed

    Bobrovs, Raitis; Acti?, Andris

    2013-11-30

    Desorption behavior of 8 different solvents from ? and ? tegafur (5-fluoro-1-(tetrahydro-2-furyl)uracil) has been studied in this work. Solvent desorption from samples stored at 95% and 50% relative solvent vapor pressure was studied in isothermal conditions at 30 C. The results of this study demonstrated that: solvent desorption rate did not differ significantly for both phases; solvent desorption in all cases occurred faster from samples with the largest particle size; and solvent desorption in most cases occurred in two steps. Structure differences and their surface properties were not of great importance on the solvent desorption rates because the main factor affecting desorption rate was sample particle size and sample morphology. Inspection of the structure packing showed that solvent desorption rate and amount of solvent adsorbed were mainly affected by surface molecule arrangement and ability to form short contacts between solvent molecule electron donor groups and freely accessible tegafur tetrahydrofuran group hydrogens, as well as between solvents molecule proton donor groups and fluorouracil ring carbonyl and fluoro groups. Solvent desorption rates of acetone, acetonitrile, ethyl acetate and tetrahydrofuran multilayers from ? and ? tegafur were approximately 30 times higher than those of solvent monolayers. Scanning electron micrographs showed that sample storage in solvent vapor atmosphere promotes small tegafur particles recrystallization to larger particles. PMID:24060368

  12. Low-temperature resource assessment program. Final report

    SciTech Connect

    Lienau, P.J.; Ross, H.

    1996-02-01

    The US Department of Energy - Geothermal Division (DOE/GD) recently sponsored the Low-Temperature Resource Assessment project to update the inventory of the nation`s low- and moderate-temperature geothermal resources and to encourage development of these resources. A database of 8,977 thermal wells and springs that are in the temperature range of 20{degrees}C to 150{degrees}C has been compiled for ten western states, an impressive increase of 82% compared to the previous assessments. The database includes location, descriptive data, physical parameters, water chemistry and references for sources of data. Computer-generated maps are also available for each state. State Teams have identified 48 high-priority areas for near-term comprehensive resource studies and development. Resources with temperatures greater than 50{degrees}C located within 8 km of a population center were identified for 271 collocated cities. Geothermal energy cost evaluation software has been developed to quickly identify the cost of geothermally supplied heat to these areas in a fashion similar to that used for conventionally fueled heat sources.

  13. 1992--1993 low-temperature geothermal assessment program, Colorada

    SciTech Connect

    Cappa, J.A.; Hemborg, H.T.

    1995-01-01

    Previous assessments of Colorado`s low-temperature geothermal resources were completed by the Colorado Geological Survey in 1920 and in the mid- to late-1970s. The purpose of the 1992--1993 low-temperature geothermal resource assessment is to update the earlier physical, geochemical, and utilization data and compile computerized databases of the location, chemistry, and general information of the low-temperature geothermal resources in Colorado. The main sources of the data included published data from the Colorado Geological Survey, the US Geological Survey WATSTOR database, and the files of the State Division of Water Resources. The staff of the Colorado Geological Survey in 1992 and 1993 visited most of the known geothermal sources that were recorded as having temperatures greater than 30{degrees}C. Physical measurements of the conductivity, pH, temperature, flow rate, and notes on the current geothermal source utilization were taken. Ten new geochemical analyses were completed on selected geothermal sites. The results of the compilation and field investigations are compiled into the four enclosed Quattro Pro 4 databases. For the purposes of this report a geothermal area is defined as a broad area, usually less than 3 sq mi in size, that may have several wells or springs. A geothermal site is an individual well or spring within a geothermal area. The 1992-1993 assessment reports that there are 93 geothermal areas in the Colorado, up from the 56 reported in 1978; there are 157 geothermal sites up from the 125 reported in 1978; and a total of 382 geochemical analyses are compiled, up from the 236 reported in 1978. Six geothermal areas are recommended for further investigation: Trimble Hot Springs, Orvis Hot Springs, an area southeast of Pagosa Springs, the eastern San Luis Valley, Rico and Dunton area, and Cottonwood Hot Springs.

  14. Analysis of the volatile organic matter of engine piston deposits by direct sample introduction thermal desorption gas chromatography/mass spectrometry.

    PubMed

    Diaby, M; Kinani, S; Genty, C; Bouchonnet, S; Sablier, M; Le Negrate, A; El Fassi, M

    2009-12-01

    This article establishes an alternative method for the characterization of volatiles organic matter (VOM) contained in deposits of the piston first ring grooves of diesel engines using a ChromatoProbe direct sample introduction (DSI) device coupled to gas chromatography/mass spectrometry (GC/MS) analysis. The addition of an organic solvent during thermal desorption leads to an efficient extraction and a good chromatographic separation of extracted products. The method was optimized investigating the effects of several solvents, the volume added to the solid sample, and temperature programming of the ChromatoProbe DSI device. The best results for thermal desorption were found using toluene as an extraction solvent and heating the programmable temperature injector from room temperature to 300 degrees C with a temperature step of 105 degrees C. With the use of the optimized thermal desorption conditions, several components have been positively identified in the volatile fraction of the deposits: aromatics, antioxidants, and antioxidant degradation products. Moreover, this work highlighted the presence of diesel fuel in the VOM of the piston deposits and gave new facts on the absence of the role of diesel fuel in the deposit formation process. Most importantly, it opens the possibility of quickly performing the analysis of deposits with small amounts of samples while having a good separation of the volatiles. PMID:19894696

  15. Ocean thermal energy conversion gas desorption studies. Volume 1. Design of experiments. [Open-cycle power systems

    SciTech Connect

    Golshani, A.; Chen, F.C.

    1980-10-01

    Seawater deaeration is a process affecting almost all proposed Ocean Thermal Energy Conversion (OTEC) open-cycle power systems. If the noncondensable dissolved air is not removed from a power system, it will accumulate in thecondenser, reduce the effectiveness of condensation, and result in deterioration of system performance. A gas desorption study is being conducted at Oak Ridge National Laboratory (ORNL) with the goal of mitigating these effects; this study is designed to investigate the vacuum deaeration process for low-temperature OTEC conditions where conventional steam stripping deaeration may not be applicable. The first in a series describing the ORNL studies, this report (1) considers the design of experiments and discusses theories of gas desorption, (2) reviews previous relevant studies, (3) describes the design of a gas desorption test loop, and (4) presents the test plan for achieving program objectives. Results of the first series of verification tests and the uncertainties encountered are also discussed. A packed column was employed in these verification tests and test data generally behaved as in previous similar studies. Results expressed as the height of transfer unit (HTU) can be correlated with the liquid flow rate by HTU = 4.93L/sup 0/ /sup 25/. End effects were appreciable for the vacuum deaeration system, and a correlation of them to applied vacuum pressure was derived.

  16. Temperature-programmed microwave-assisted synthesis of SBA-15 ordered mesoporous silica.

    PubMed

    Celer, Ewa B; Jaroniec, Mietek

    2006-11-01

    The currently available microwave technology permits the development and implementation of a temperature-programmed microwave-assisted synthesis (TPMS) of ordered mesoporous silicas (OMSs). Unlike in previously reported syntheses of OMSs, in which only the final hydrothermal treatment was carried out under microwave irradiation, this work takes advantage of the existing capabilities of modern microwave systems to program the temperature and time for the entire synthesis of these materials. To demonstrate the flexibility of the proposed microwave-assisted synthesis, besides programming two consecutive steps involving initial stirring of the gel at a lower temperature and static hydrothermal treatment at a higher temperature, we explored the possibility of temperature programming of the latter step. A major advantage of microwave technology is the feasibility of temperature and time programming, which has been demonstrated by the synthesis of one of the most popular OMSs, SBA-15, over an unprecedented range of temperatures from 40 to 200 degrees C. Since the synthesis of OMSs has not yet been explored and reported at temperatures exceeding 150 degrees C, this work is focused on the SBA-15 samples prepared at higher temperatures (such as 160, 180, and even 200 degrees C). These SBA-15 samples show better thermal stability than those synthesized at commonly used temperatures either under conventional or microwave conditions. Moreover, a partial decomposition of the template during high-temperature microwave-assisted syntheses does not compromise the formation of well-ordered SBA-15 materials. This study shows that the simplicity and capability of temperature and time programming in TPMS allows one not only to tune the adsorption and structural properties of OMSs but also to easily screen a wide range of conditions in order to optimize and scale-up their preparation as well as to significantly reduce the time of synthesis from days to hours. PMID:17076515

  17. Programming Enhancements for Low Temperature Thermal Decomposition Workstation

    SciTech Connect

    Igou, R.E.

    1998-10-01

    This report describes a new control-and-measurement system design for the Oak Ridge Y-12 Plant's Low Temperature Thermal Decomposition (LTTD) process. The new design addresses problems with system reliability stemming from equipment obsolescence and addresses specific functional improvements that plant production personnel have identified, as required. The new design will also support new measurement techniques, which the Y-12 Development Division has identified for future operations. The new techniques will function in concert with the original technique so that process data consistency is maintained.

  18. Heavy-ion induced desorption yields of cryogenic surfaces bombarded with 4.2MeV/u lead ions

    NASA Astrophysics Data System (ADS)

    Mahner, E.; Evans, L.; Kchler, D.; Scrivens, R.; Bender, M.; Kollmus, H.; Severin, D.; Wengenroth, M.

    2011-05-01

    The ion-induced desorption experiment, installed in the CERN Heavy-Ion Accelerator LINAC 3, has been used to study the dynamic outgassing of cryogenic surfaces. Two different targets, bare and gold-coated copper, were bombarded under perpendicular impact with 4.2MeV/u Pb54+ ions. Partial pressure rises of H2, CH4, CO, and CO2 and effective desorption yields were measured at 300, 77, and 6.3 K using single shot and continuous ion bombardment techniques. We find that the heavy-ion-induced desorption yield is temperature dependent and investigate the influence of CO gas cryosorbed at 6.3 K. The gain in desorption yield reduction at cryogenic temperature vanishes after several monolayers of CO are cryosorbed on both targets. In this paper we describe the new cryogenic target assembly, the temperature-dependent pressure rise, desorption yield, and gas adsorption measurements.

  19. Adsorption, Desorption, and Clustering H20 on Pt (111)

    SciTech Connect

    Daschbach, John L.; Peden, Brandon M.; Smith, R. Scott; Kay, Bruce D.

    2004-01-15

    The adsorption, desorption, and clustering behavior of H20 on Pt(111) has been investigated by specular He scattering. The data show that water adsorbed on a clean Pt(111) surface undergoes a transition from a random to a clustered structure near 60 K. The initial helium scattering cross sections as a function of temperature are found to be insensitive to H20 flux over a range of 0.005 ML/s to 0.55 ML/s indicating the clustering process is more complex than simple surface diffusion. The coarsening process of an initially random distribution of water deposited at 25 K is found to occur over a broad temperature range, 60 K< T <140 K, during thermal annealing. The desorption kinetics for submonolayer water are determined to be zero-order for surface coverages greater than 0.05 ML and temperatures between 150 K and 174 K. The zero-order desorption kinetics are consistent with a two-dimensional two-phase coexistence between H2O condensed phase and a 2-gas phase on the Pt surface

  20. Thermal desorption spectrometry for identification of products formed by electron-induced reactions

    NASA Astrophysics Data System (ADS)

    Burean, E.; Ipolyi, I.; Hamann, T.; Swiderek, P.

    2008-11-01

    Thermal desorption spectra of thin films of acetaldehyde and hexamethyldisiloxane were recorded before and after exposure to electrons with an energy of 15 eV to monitor the formation of the products CO, propionaldehyde, and methane. While the identification of the products in previous work reported in literature has relied on a comparison with desorption temperatures of pure multilayer films, it is proposed here to compare with reference samples containing specific amounts of the anticipated product. It is shown that this approach is more accurate because the desorption temperatures can be modified considerably by a molecular matrix or by coadsorbates. Also trapping of the products within a molecular film can occur and lead to a delayed desorption as exemplified by the production of methane in thin films of hexamethyldisiloxane.

  1. Low energy electron stimulated desorption from DNA films dosed with oxygen

    SciTech Connect

    Mirsaleh-Kohan, Nasrin; Bass, Andrew D.; Cloutier, Pierre; Massey, Sylvain; Sanche, Leon

    2012-06-21

    Desorption of anions stimulated by 1-18 eV electron impact on self-assembled monolayer (SAM) films of single DNA strands is measured as a function of film temperature (50-250 K). The SAMs, composed of 10 nucleotides, are dosed with O{sub 2}. The OH{sup -} desorption yields increase markedly with exposure to O{sub 2} at 50 K and are further enhanced upon heating. In contrast, the desorption yields of O{sup -}, attributable to dissociative electron attachment to trapped O{sub 2} molecules decrease with heating. Irradiation of the DNA films prior to the deposition of O{sub 2} shows that this surprising increase in OH{sup -} desorption, at elevated temperatures, arises from the reaction of O{sub 2} with damaged DNA sites. These results thus appear to be a manifestation of the so-called 'oxygen fixation' effect, well known in radiobiology.

  2. Tritium release and trapping in austenitic stainless steels: Role of microstructure and desorption anneal

    SciTech Connect

    Chene, J.

    2008-07-15

    The behavior of hydrogen and its isotopes in materials is a major concern in future nuclear systems both for the predictive analysis of the role of H, D, T in the environmental degradation of structural materials, for the confinement and inventory of tritium, and for the management of tritiated wastes. This study is focused on the characterization of the effect of the alloy microstructure, of desorption anneal and of oxide films on the tritium behavior (desorption kinetics, trapping, residual concentration) in various austenitic stainless steels. Different techniques (high temperature extraction of hydrogen, beta counting of tritium in massive samples) were used to study: the tritium absorption and desorption in several stainless steels, the role of the annealing conditions (temperature/time) on the tritium residual concentration and desorption flow, and the role of microstructural defects and of oxide films on the diffusion and trapping of tritium. (authors)

  3. High Temperature Materials Laboratory User Program: 19th Annual Report, October 1, 2005 - September 30, 2006

    SciTech Connect

    Pasto, Arvid

    2007-08-01

    Annual Report contains overview of the High Temperature Materials Laboratory User Program and includes selected highlights of user activities for FY2006. Report is submitted to individuals within sponsoring DOE agency and to other interested individuals.

  4. Air separation with temperature and pressure swing

    DOEpatents

    Cassano, Anthony A. (Allentown, PA)

    1986-01-01

    A chemical absorbent air separation process is set forth which uses a temperature swing absorption-desorption cycle in combination with a pressure swing wherein the pressure is elevated in the desorption stage of the process.

  5. On gas desorption from the tokamak first wall during edge localized modes

    SciTech Connect

    Marenkov, E. D.; Smirnov, R. D.; Krasheninnikov, S. I.

    2013-11-15

    The effect of gas desorption from the tokamak first wall on the pedestal recovery in the H-mode after an edge-localized-mode burst is considered. Results of FACE code simulations of hydrogen desorption from a beryllium wall are presented. It is found that the wall has a significant effect on plasma processes only at sufficiently low temperatures (of about 400 K), which agrees with qualitative estimates obtained earlier in the zero-dimensional approximation.

  6. Effects of programming and healing temperatures on the healing efficiency of a confined healable polymer composite

    NASA Astrophysics Data System (ADS)

    Yougoubare, Y. Quentin; Pang, Su-Seng

    2014-02-01

    In previous work, a biomimetic close-then-heal (CTH) healing mechanism was proposed and validated to repeatedly heal wide-open cracks in load carrying engineering structures by using constrained expansion of compression programmed thermoset shape memory polymers (SMPs). In this study, the effects on healing efficiencies of variation of temperature during both thermomechanical programming and shape recovery (healing) under three-dimensional (3D) confinement are evaluated. The polymer considered is a polystyrene shape memory polymer with 6% by volume of thermoplastic particle additives (copolyester) dispersed in the matrix. In addition to the programming and healing temperatures, some of the parameters investigated include the flexural strength, crack width and elemental composition at the crack interface. It is observed that while increase of the programming temperature is slightly beneficial to strength recovery, most of the strength recovered and damage repair are strongly dependent on the healing temperature. The best healing efficiency (63%) is achieved by a combination of a programming temperature above the glass transition temperature of the polymer and a healing temperature above the bonding point of the copolyester.

  7. The Generation of Surface-bound Exospheres via Electron-Stimulated Desorption (and Related Phenomena): Results from Apollo samples and Hermian Regolith Simulants

    NASA Astrophysics Data System (ADS)

    Bennett, C.; Poston, M.; McLain, J. L.; Orlando, T. M.

    2014-12-01

    The generation of surface-bound exospheres present around the Moon, Mercury and other airless rocky bodies are produced primarily by the interaction of micrometeoroid impacts and charged particles from the solar wind, and magnetospheres with those surfaces. While the study of the interactions of both micrometeoroids and ion sputtering are well investigated, the contributions arising from energetic electron interactions are typically less-well established. Observations from the Fast Imaging Plasma Spectrometer (FIPS), taken < 400 km from the surface, have shown a plasma cusp with energetic heavy ions (i.e. Na+- and O+-groups) for which the source has not been determined. However, the precipitation of keV electrons onto the surfaces of Mercury has recently been inferred from measurements using the X-Ray Spectrometer (XRS) instrument onboard the MESSENGER spacecraft observations of the night-side of Mercury. A newly developed global kinetic transport model suggests that electron-stimulated desorption (ESD), and possibly light ion stimulated desorption (ISD), can directly yield ions that can be transported and dynamically accelerated to the plasma cusp regions observed by FIPS. In addition, keV electrons and ions from the solar wind and Earth's magnetosphere frequently bombard with the lunar surface. Here, we present some of the most recent results from our ongoing work studying the effects of photon-stimulated desorption (PSD), ion-stimulated desorption (ISD) and implantation, as well as electron-stimulated desorption (ESD). Apollo samples collected from both the lunar highland and Mare regions, as well as simulants of the Mercury Regolith have been investigated. The temperature- (100-600 K) and energy-dependence (threshold - 2 keV) of ESD time-of-flight (ToF) results will be presented for these materials along with some preliminary results from our group based on photon-desorption studies of water on lunar material, temperature-programmed desorption (TPD) studies of water covered regolith and dusts, as well as the effects of ion implantation/sputtering using keV H+ ions on ESD-ToF results. The implications of these results in the context of current observations will be discussed.

  8. High temperature thermocouple development program, part A and part B

    NASA Technical Reports Server (NTRS)

    Toenshoff, D. A.; Zysk, E. D.; Fleischner, P. L.

    1972-01-01

    The problem of extending the useful life of thermocouples intended for in-core and out-of-core thermionic applications in a vacuum environment at temperatures up to 2273 K for periods of time up to 10,000 hours was investigated. Many factors that may influence this useful life were examined, and a basic probe design was developed. With a few modifications, twenty-three thermocouple assemblies were fabricated. Generally the finished thermocouple consisted of solid doped W-3% Re and W-25% Re wires and high purity and high density BeO insulators, and was sheathed in a high purity tantalum tube. In a few probes, stranded thermocouple wires were substituted; commercial grade BeO was used; and in two cases, CVD W-22% Re tubing was used. Each of the components was made of the highest purity materials available; was subjected to special cleaning steps, and was assembled in a class 10,000 clean room. Pertinent physical and chemical properties were determined on each of the components. Special processing techniques were used in the fabrication of the high purity (99.95%), high density (over 95% of theoretical) BeO.

  9. Computer program simplifies transient and steady-state temperature prediction for complex body shapes

    NASA Technical Reports Server (NTRS)

    Giebler, K. N.

    1966-01-01

    Computer program evaluates heat transfer modes and calculates either the transient or steady-state temperature distributions throughout an object of complex shape when heat sources are applied to specified points on the object. It uses an electrothermal model to simulate the conductance, heat capacity, and temperature potential of the object.

  10. Diurnal Soil Temperature Effects within the Globe[R] Program Dataset

    ERIC Educational Resources Information Center

    Witter, Jason D.; Spongberg, Alison L.; Czajkowski, Kevin P.

    2007-01-01

    Long-term collection of soil temperature with depth is important when studying climate change. The international program GLOBE[R] provides an excellent opportunity to collect such data, although currently endorsed temperature collection protocols need to be refined. To enhance data quality, protocol-based methodology and automated data logging,…

  11. Diurnal Soil Temperature Effects within the Globe[R] Program Dataset

    ERIC Educational Resources Information Center

    Witter, Jason D.; Spongberg, Alison L.; Czajkowski, Kevin P.

    2007-01-01

    Long-term collection of soil temperature with depth is important when studying climate change. The international program GLOBE[R] provides an excellent opportunity to collect such data, although currently endorsed temperature collection protocols need to be refined. To enhance data quality, protocol-based methodology and automated data logging,

  12. Adsorption and desorption of H 2O on potassium precovered Si(100)2 1 surface

    NASA Astrophysics Data System (ADS)

    Hongo, Shozo; Taniguchi, Shinichi; Ojima, Kaoru; Urano, Toshio; Kanaji, Toru

    1994-12-01

    The adsorption and desorption of H 2O on a potassium precovered Si(100)2 1 surface have been studied using MDS (metastable deexcitation spectroscopy) and TDS (thermal desorption spectroscopy). It is concluded that H 2O is dissociatively attached to a 1 ML K/Si(100)21 surface as OH and H at a dosing less than 1 langmuir at room temperature, because no molecularly adsorbed H 2O is observed either by MDS or by TDS. The thermal desorption spectrum of H 2 (mass 2) consists of two peaks. The lower temperature peak at 140C is attributed to the hydrogen of a OH species bound to a Si atom. The higher temperature peak at 510C is caused by hydrogen bound to Si dangling bonds. The thermal desorption spectrum of SiO (mass 44) has two peaks. The SiO desorption peak at 280C suggests that bonds weaker than the usual SiO 2 bonds exist. A detailed description of the adsorption and desorption of H 2O is given by comparing both spectra of MDS and TDS and a model is proposed.

  13. Synthesis of alcohols from carbon oxides and hydrogen. VIII. A temperature-programmed reaction study of n-butanal on a Zn-Cr-O catalyst

    SciTech Connect

    Lietti, L.; Botta, D.; Forzatti, P.; Mantica, E.; Tronconi, E.; Pasquon, I.

    1988-06-01

    The interaction of n-butanal with a Zn-Cr-O catalyst has been studied by temperature-programmed reaction. Using combined GC, GC-FTIR, and GC-MS techniques, a large number of desorption products have been identified, including 1-butanol, C/sub 8/ and C/sub 12/ aldehydes, C/sub 7/ and C/sub 8/ ketones, and C/sub 3/, C/sub 4/, and C/sub 7/ olefins, as well as CO/sub 2/, dienes, trienes, aromatics, and light hydrocarbons. The formation of most products is explained by assuming surface reactions of two classes of intermediate species originating from the adsorption of n-butanal and from the surface aldol-like condensation of two molecules of n-butanal. Results indicate that the Zn-Cr oxide catalyst is active in performing aldehyde condensation, hydrogenation, hydrolysis, dehydrogenation, decarboxylation, and dehydration, along with isomerization and cracking reactions. Different functionalities are associated with different temperature ranges. The detected chemical functionalities are discussed with respect to their relevance to the direct synthesis of methanol and higher alcohols from CO and H/sub 2/.

  14. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    PubMed Central

    2012-01-01

    The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (?H0, ?S0, and ?G0) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment. PMID:22269298

  15. Fortran computer programs to plot and process aquifer pressure and temperature data

    USGS Publications Warehouse

    Czarnecki, J.B.

    1983-01-01

    Two FORTRAN computer programs have been written to process water-well temperature and pressure data recorded automatically by a datalogger on magnetic tape. These programs process the data into tabular and graphical form. Both programs are presented with documentation. Sample plots of temperature versus time, water levels versus time, aquifer pressure versus log time , log drawdown versus log 1/time, and log drawdown versus log time/radius squared are presented and are obtained using standard CALCOM directives. Drawdown plots may be used directly to obtain aquifer transmissivities and storage coefficients as well as leakance coefficients. (USGS)

  16. Patterning graphene at the nanometer scale via hydrogen desorption.

    SciTech Connect

    Sessi, P.; Guest, J. R.; Bode, M.; Guisinger, N.; Center for Nanoscale Materials; Politecnico di Milano

    2009-12-01

    We have demonstrated the reversible and local modification of the electronic properties of graphene by hydrogen passivation and subsequent electron-stimulated hydrogen desorption with an scanning tunneling microscope tip. In addition to changing the morphology, we show that the hydrogen passivation is stable at room temperature and modifies the electronic properties of graphene, opening a gap in the local density of states. This insulating state is reversed by local desorption of the hydrogen, and the unaltered electronic properties of graphene are recovered. Using this mechanism, we have 'written' graphene patterns on nanometer length scales. For patterned regions that are roughly 20 nm or greater, the inherent electronic properties of graphene are completely recovered. Below 20 nm we observe dramatic variations in the electronic properties of the graphene as a function of pattern size. This reversible and local mechanism for modifying the electronic properties of graphene has far-reaching implications for nanoscale circuitry fabricated from this revolutionary material.

  17. Energetic particle induced desorption of water vapor cryo-condensate

    SciTech Connect

    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 {times} 10{sup 10} cm{sup {minus}3}, electron temperature = 3 eV). Significant desorption of the condensate occurred, suggesting that impingement of energeticparticles (10 eV) at flux levels of {approximately}10{sup 16} cm{sup 2}s{sup {minus}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.

  18. Femtosecond laser induced desorption of water from silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Kwiet, S.; Starr, D. E.; Grujic, A.; Wolf, M.; Hotzel, A.

    2005-01-01

    The photodesorption mechanism of H2O from quartz-supported silver nanoparticles has been studied by femtosecond laser two-pulse correlation and fluence dependence measurements. With the laser wavelength close to the maximum of the (1,1) plasmon resonance of the nanoparticles, the desorption was found to be purely thermal, i.e., induced by coupling of the desorption coordinate to the nanoparticle lattice temperature, both in the low- and the high-coverage regimes. The lattice cooling times of the nanoparticles are in the range of several hundred ps, in accordance with recent time-resolved X-ray measurements. Also observed is a reversible red-shift of the nanoparticle plasmon modes with increasing H2O coverage which is attributed to dielectric screening.

  19. Hydrogen absorption-desorption properties of U 2Ti

    NASA Astrophysics Data System (ADS)

    Takuya, Yamamoto; Satoru, Tanaka; Michio, Yamawaki

    1990-02-01

    Hydrogen absorption-desorption properties of U 2Ti 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, cH, reaches 2.4 H atoms/F.U. In the second plateau, UH 3 is formed and cH 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 2H 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.

  20. Desorption induced by multiple electronic transitions

    NASA Astrophysics Data System (ADS)

    Misewich, J. A.; Heinz, T. F.; Newns, D. M.

    1992-06-01

    A new mechanism is introduced to describe desorption from surfaces under conditions of strong electronic excitation. When repetitive excitations occur within the relaxation time for the adsorbate-surface vibration, the process of desorption induced by multiple electronic transitions may provide an enhancement of orders of magnitude over a single-excitation mechanism. This generalization of the classic Menzel-Gomer-Redhead picture encompasses within one formalism both single-excitation processes and a thermal limit. The mechanism may be operative in desorption by femtosecond laser pulses.

  1. Gas desorption during friction of amorphous carbon films

    NASA Astrophysics Data System (ADS)

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

    2008-03-01

    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 H2 and CH4. 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 was found that temperature rise during friction is short-term and not significant. The number of desorbed molecules due to frictional heating was calculated.

  2. THERMTRAJ: A FORTRAN program to compute the trajectory and gas film temperatures of zero pressure balloons

    NASA Technical Reports Server (NTRS)

    Horn, W. J.; Carlson, L. A.

    1983-01-01

    A FORTRAN computer program called THERMTRAJ is presented which can be used to compute the trajectory of high altitude scientific zero pressure balloons from launch through all subsequent phases of the balloon flight. In addition, balloon gas and film temperatures can be computed at every point of the flight. The program has the ability to account for ballasting, changes in cloud cover, variable atmospheric temperature profiles, and both unconditional valving and scheduled valving of the balloon gas. The program was verified for an extensive range of balloon sizes (from 0.5 to 41.47 million cubic feet). Instructions on program usage, listing of the program source deck, input data and printed and plotted output for a verification case are included.

  3. Flight summaries and temperature climatology at airliner cruise altitudes from GASP (Global Atmospheric Sampling Program) data

    NASA Technical Reports Server (NTRS)

    Nastrom, G. D.; Jasperson, W. H.

    1983-01-01

    Temperature data obtained by the Global Atmospheric Sampling Program (GASP) during the period March 1975 to July 1979 are compiled to form flight summaries of static air temperature and a geographic temperature climatology. The flight summaries include the height and location of the coldest observed temperature and the mean flight level, temperature and the standard deviation of temperature for each flight as well as for flight segments. These summaries are ordered by route and month. The temperature climatology was computed for all statistically independent temperture data for each flight. The grid used consists of 5 deg latitude, 30 deg longitude and 2000 feet vertical resolution from FL270 to FL430 for each month of the year. The number of statistically independent observations, their mean, standard deviation and the empirical 98, 50, 16, 2 and .3 probability percentiles are presented.

  4. The desorption of toluene from a montmorillonite clay adsorbent in a rotary kiln environment

    SciTech Connect

    Owens, W.D.; Silcox, G.D.; Lighty, J.S.; Xiao Xue Deng; Pershing, D.W. ); Cundy, V.A.; Leger, C.B.; Jakway, A.L. )

    1992-05-01

    The vaporization of toluene from pre-dried, 3 mm montmorillonite clay particles was studied in a 130 kW pilot-scale rotary kiln with inside dimensions of 0.61 by 0.61 meters. Vaporization rates were obtained with a toluene weight fraction of 0.25 percent as a function of kiln fill fractions from 3 to 8 percent, rotation rates from 0.1 to 0.9 rpm, and kiln wall temperatures from 189 to 793 C. Toluene desorption rates were obtained from gas-phase measurements and interpreted using a desorption model that incorporates the slumping frequency of the solids, the fill fraction of the kiln, the diffusion of toluene in the bed, and the rate of particle desorption using an Arrhenius-type expression that is a function of bed temperature and average bed concentration. The model included three adjustable desorption parameters which were obtained by fitting the experimental data at one set of conditions with a least squares technique. Solid and kiln-wall temperatures were continuously recorded and used in the model at predicting the effects of fill fraction and rotation rate over a range of temperatures. A methodology for predicting full-scale performance was developed. Full-scale toluene desorption predictions were completed for different operating temperatures.

  5. Behaviour of neutron irradiated beryllium during temperature excursions up to and beyond its melting temperature

    NASA Astrophysics Data System (ADS)

    Pajuste, Elina; Kizane, Gunta; Avotiņa, Līga; Zariņš, Artūrs

    2015-10-01

    Beryllium pebble behaviour has been studied regarding the accidental operation conditions of tritium breeding blanket of fusion reactors. Structure evolution, oxidation and thermal properties have been compared for nonirradiated and neutron irradiated beryllium pebbles during thermal treatment in a temperature range from ambient temperature to 1600 K. For neutron irradiated pebbles tritium release process was studied. Methods of temperature programmed tritium desorption (TPD) in combination with thermogravimetry (TG) and temperature differential analysis (TDA), scanning electron microscopy (SEM) in combination with Energy Dispersive X-ray analysis (EDX) have been used. It was found that there are strong relation between tritium desorption spectra and structural evolution of neutron irradiated beryllium. The oxidation rate is also accelerated by the structure damages caused by neutrons.

  6. Plasma Desorption Mass Spectrometry: Coming of Age.

    ERIC Educational Resources Information Center

    Cotter, Robert J.

    1988-01-01

    Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

  7. Remaining coverage in associative desorption process

    NASA Astrophysics Data System (ADS)

    Furlong, O.; Manzi, S.; Costanza, G.; Pereyra, V. D.

    2004-08-01

    In this paper the kinetic of dissociative adsorption of dimers followed by associative desorption is analyzed. The coupled differential equations which describe the kinetics of the process were obtained by applying the so-called local evolution rules. Particular interest presents the irreversible desorption process. In fact, given that desorption proceeds from the reacting nearest-neighbor monomers, a remaining coverage results from those isolated particles when the mobility is neglected, therefore, the resulting configuration can be considered as a jamming state of the system. The exact solution for the remaining coverage is obtained in one-dimensional chain, where the effect of the lateral interactions are also included. The two-dimensional case is analyzed by using Monte Carlo simulation. The equilibrium solutions and the thermal desorption spectra are also studied.

  8. VAC*TRAX - Thermal desorption for mixed wastes

    SciTech Connect

    McElwee, M.J.; Palmer, C.R.

    1995-12-01

    The patented VAC*TRAX process was designed in response to the need to remove organic constituents from mixed waste, waste that contains both a hazardous (RCRA or TSCA regulated) component and a radioactive component. Separation of the mixed waste into its hazardous and radioactive components allows for ultimate disposal of the material at existing, permitted facilities. The VAC*TRAX technology consists of a jacketed vacuum dryer followed by a condensing train. Solids are placed in the dryer and indirectly heated to temperatures as high as 260{degrees}C, while a strong vacuum (down to 50 mm Hg absolute pressure) is applied to the system and the dryer is purged with a nitrogen carrier gas. The organic contaminants in the solids are thermally desorbed, swept up in the carrier gas and into the condensing train where they are cooled and recovered. The dryer is fitted with a filtration system that keeps the radioactive constituents from migrating to the condensate. As such, the waste is separated into hazardous liquid and radioactive solid components, allowing for disposal of these streams at a permitted incinerator or a radioactive materials landfill, respectively. The VAC*TRAX system is designed to be highly mobile, while minimizing the operational costs with a simple, robust process. These factors allow for treatment of small waste streams at a reasonable cost. This paper describes the VAC*TRAX thermal desorption process, as well as results from the pilot testing program. Also, the design and application of the full-scale treatment system is presented. Materials tested to date include spiked soil and debris, power plant trash and sludge contaminated with solvents, PCB contaminated soil, solvent-contaminated uranium mill-tailings, and solvent and PCB-contaminated sludge and trash. Over 70 test runs have been performed using the pilot VAC*TRAX system, with more than 80% of the tests using mixed waste as the feed material.

  9. Thermal desorption of PCB-contaminated soil with sodium hydroxide.

    PubMed

    Liu, Jie; Qi, Zhifu; Zhao, Zhonghua; Li, Xiaodong; Buekens, Alfons; Yan, Jianhua; Ni, Mingjiang

    2015-12-01

    The thermal desorption was combined with sodium hydroxide to remediate polychlorinated biphenyl (PCB)-contaminated soil. The experiments were conducted at different temperatures ranging from 300 to 600C with three NaOH contents of 0.1, 0.5, and 1%. The results showed that thermal desorption was effective for PCB removal, destruction, and detoxication, and the presence of NaOH enhanced the process by significant dechlorination. After treatment with 0.1% NaOH, the removal efficiency (RE) increased from 84.8% at 300C to 98.0% at 600C, corresponding to 72.7 and 91.7% of destruction efficiency (DE). With 1% NaOH content treated at 600C, the RE and DE were 99.0 and 93.6%, respectively. The effect of NaOH content on PCB removal was significant, especially at lower temperature, yet it weakened under higher temperature. The interaction between NaOH content and temperature influenced the PCB composition. The higher temperature with the help of NaOH effectively increased the RE and DE of 12 dioxin-like PCBs (based on WHO-TEQ). PMID:26263886

  10. H2 adsorption on multiwalled carbon nanotubes at low temperatures and low pressures

    NASA Astrophysics Data System (ADS)

    Xu, F.; Barberio, M.; Vasta, R.; Barone, P.; Bonanno, A.; Pirronello, V.

    2008-11-01

    We present an experimental study on H2 adsorption on multiwalled carbon nanotubes (MWCNTs) at low temperatures (12-30 K) and low pressures (210-5Torr) using the temperature programmed desorption technique. Our results show that the molecular hydrogen uptake increases nearly exponentially from 610-9wt.% at 24.5 K to 210-7wt.% at 12.5 K and that the desorption kinetics is of the first order. Comparative measurements indicate that MWCNTs have an adsorption capacity about two orders higher than that of activated carbon (charcoal) making them a possible candidate as hydrogen cryosorber for eventual applications in accelerators and synchrotrons.

  11. [Optimized linear temperature programming for capillary gas chromatography by the method of gridding search].

    PubMed

    Lin, T; Lei, G H

    2001-01-01

    Linear temperature programming of capillary gas chromatography was optimized by using a new method of gridding search. A point of gridding demonstrated a condition of temperature programmed and the resolution and the retention time were optimized at all gridding points. With a new design of calculation, the method not only considered directly all components that were separated, but the velocity of calculation was improved also. Twenty-one compounds of alkanes, alcohols, halo-hydrocarbons and aromatic hydrocarbons, of which Kovats Indexes are varying from 600 to 1,000, were separated by this new method on an OV-101 column under linear temperature programming. Good results were obtained. The time for optimizing the 21 compounds was less than 1 min. PMID:12541845

  12. Modelling of discrete TDS-spectrum of hydrogen desorption

    NASA Astrophysics Data System (ADS)

    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.

  13. Desorption of oxygen from alloyed Ag/Pt(111)

    SciTech Connect

    Jankowski, Maciej; Wormeester, Herbert Zandvliet, Harold J. W.; Poelsema, Bene

    2014-06-21

    We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (E{sub des}) decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of E{sub des} with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.

  14. Novel devices for solvent delivery and temperature programming designed for capillary liquid chromatography.

    PubMed

    Coutinho, Lincoln Figueira Marins; Nazario, Carlos Eduardo Domingues; Monteiro, Alessandra Maffei; Lanas, Fernando Mauro

    2014-08-01

    Analyses in chromatographic systems able to save mobile and stationary phases without reducing efficiency and resolution are of current interest. These advantages regarding savings have challenged us to develop a system dedicated to miniaturized liquid chromatography. This paper reports on the development of a high-pressure syringe-type pump, an oven able to perform isothermal and temperature programming and a software program to control these chromatographic devices. The experimental results show that the miniaturized system can generate reproducible and accurate temperature and flow rate. The system was applied to the separation of statins and tetracylines and showed excellent performance. PMID:24838528

  15. Determination of surface coverage of catalysts: Temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    SciTech Connect

    Broek, A.C.M. van den; Grondelle, J. van; Santen, R.A. van

    1999-07-25

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity measurements that both catalysts lose activity as a function of time on stream due to inhibition of the surface by reaction intermediates. The used catalysts were studied by XPS and temperature programmed techniques. It was found that the surface of the catalysts had a high coverage of NH and OH and some additional NH{sub 2}. It seems most likely that the reaction mechanism proceeds through a stepwise dehydrogenation of the ammonia molecule. It appears that the last dehydrogenation step (NH by OH to N and water) is the rate determining step. The high selectivity of iridium to nitrogen can be explained by the higher activity of iridium in dissociating NO.

  16. AISI/DOE Advanced Process Control Program Vol. 6 of 6: Temperature Measurement of Galvanneal Steel

    SciTech Connect

    S.W. Allison; D.L. Beshears; W.W. Manges

    1999-06-30

    This report describes the successful completion of the development of an accurate in-process measurement instrument for galvanneal steel surface temperatures. This achievement results from a joint research effort that is a part of the American Iron and Steel Institute's (AISI) Advanced Process Control Program, a collaboration between the U.S> Department of Energy and fifteen North American Steelmakers. This three-year project entitled ''Temperature Measurement of Galvanneal Steel'' uses phosphor thermography, and outgrowth of Uranium enrichment research at Oak Ridge facilities. Temperature is the controlling factor regarding the distribution of iron and zinc in the galvanneal strip coating, which in turn determines the desired product properties

  17. Photon-stimulated desorption as a substantial source of sodium in the lunar atmosphere.

    PubMed

    Yakshinskiy, B V; Madey, T E

    1999-08-12

    Mercury and the Moon both have tenuous atmospheres that contain atomic sodium and potassium. These chemicals must be continuously resupplied, as neither body can retain the atoms for more than a few hours. The mechanisms proposed to explain the resupply include sputtering of the surface by the solar wind, micrometeorite impacts, thermal desorption and photon-stimulated desorption. But there are few data and no general agreement about which processes dominate. Here we report laboratory studies of photon-stimulated desorption of sodium from surfaces that simulate lunar silicates. We find that bombardment of such surfaces at temperatures of approximately 250 K by ultraviolet photons (wavelength lambda < 300 nm) causes very efficient desorption of sodium atoms, induced by electronic excitations rather than by thermal processes or momentum transfer. The flux at the lunar surface of ultraviolet photons from the Sun is sufficient to ensure that photon-stimulated desorption of sodium contributes substantially to the Moon's atmosphere. On Mercury, solar heating of the surface implies that thermal desorption will also be an important source of atmospheric sodium. PMID:10458159

  18. Film growth, adsorption and desorption kinetics of indigo on SiO2

    NASA Astrophysics Data System (ADS)

    Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

    2014-05-01

    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.

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

    SciTech Connect

    Scherwitzl, Boris Resel, Roland; Winkler, Adolf

    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.

  20. Determination of the Arrhenius Activation Energy Using a Temperature-Programmed Flow Reactor.

    ERIC Educational Resources Information Center

    Chan, Kit-ha C.; Tse, R. S.

    1984-01-01

    Describes a novel method for the determination of the Arrhenius activation energy, without prejudging the validity of the Arrhenius equation or the concept of activation energy. The method involves use of a temperature-programed flow reactor connected to a concentration detector. (JN)

  1. Testing program for concrete at temperatures to 894/sup 0/K. [LMFBR

    SciTech Connect

    Naus, D.J.; Oland, C.B.; Robinson, G.C.

    1981-01-01

    A test program was conducted to define the variations in mechanical properties of a limestone aggregate concrete and a lightweight insulating concrete exposed to elevated temperatures. Four test series were conducted: (1) unconfined compression; (2) shear; (3) rebar bond; and (4) sustained loading (creep). Tests results are presented.

  2. An Application of Trimethylsilyl Derivatives with Temperature Programmed Gas Chromatography to the Senior Analytical Laboratory.

    ERIC Educational Resources Information Center

    Kelter, Paul B.; Carr, James D.

    1983-01-01

    Describes an experiment designed to teach temperature programed gas chromatography (TPGC) techniques and importance of derivatizing many classes of substrated to be separated. Includes equipment needed, procedures for making trimethylsilyl derivatives, applications, sample calculations, and typical results. Procedure required one, three-hour

  3. Computer program determines thermal environment and temperature history of lunar orbiting space vehicles

    NASA Technical Reports Server (NTRS)

    Head, D. E.; Mitchell, K. L.

    1967-01-01

    Program computes the thermal environment of a spacecraft in a lunar orbit. The quantities determined include the incident flux /solar and lunar emitted radiation/, total radiation absorbed by a surface, and the resulting surface temperature as a function of time and orbital position.

  4. Advanced High Temperature Polymer Matrix Composites for Gas Turbine Engines Program Expansion

    NASA Technical Reports Server (NTRS)

    Hanley, David; Carella, John

    1999-01-01

    This document, submitted by AlliedSignal Engines (AE), a division of AlliedSignal Aerospace Company, presents the program final report for the Advanced High Temperature Polymer Matrix Composites for Gas Turbine Engines Program Expansion in compliance with data requirements in the statement of work, Contract No. NAS3-97003. This document includes: 1 -Technical Summary: a) Component Design, b) Manufacturing Process Selection, c) Vendor Selection, and d) Testing Validation: 2-Program Conclusion and Perspective. Also, see the Appendix at the back of this report. This report covers the program accomplishments from December 1, 1996, to August 24, 1998. The Advanced High Temperature PMC's for Gas Turbine Engines Program Expansion was a one year long, five task technical effort aimed at designing, fabricating and testing a turbine engine component using NASA's high temperature resin system AMB-21. The fiber material chosen was graphite T650-35, 3K, 8HS with UC-309 sizing. The first four tasks included component design and manufacturing, process selection, vendor selection, component fabrication and validation testing. The final task involved monthly financial and technical reports.

  5. Photon stimulated desorption from oxidized Al(110). [Surface hydroxyls

    SciTech Connect

    Johnson, E.D.; Garrett, R.F.; Knotek, M.L.; Sette, F.

    1987-01-01

    We have studied oxide films on Al(110) by photon stimulated desorption (PSD) on the Bell Labs U4 PGM at the National Synchrotron Light Source. Utilizing a time of flight technique we have obtained ion energy distribution (IED) and relative ion yield (RIY) data at the Al 2p and O 1s edges for oxides prepared at various temperatures. These initial studies suggest that different sites for the surface hydroxyls exist, that they can be selectively prepared, and examined by PSD. 15 refs., 9 figs.

  6. Computer Program for Calculation of a Gas Temperature Profile by Infrared Emission: Absorption Spectroscopy

    NASA Technical Reports Server (NTRS)

    Buchele, D. R.

    1977-01-01

    A computer program to calculate the temperature profile of a flame or hot gas was presented in detail. Emphasis was on profiles found in jet engine or rocket engine exhaust streams containing H2O or CO2 radiating gases. The temperature profile was assumed axisymmetric with an assumed functional form controlled by two variable parameters. The parameters were calculated using measurements of gas radiation at two wavelengths in the infrared. The program also gave some information on the pressure profile. A method of selection of wavelengths was given that is likely to lead to an accurate determination of the parameters. The program is written in FORTRAN IV language and runs in less than 60 seconds on a Univac 1100 computer.

  7. THE HIGH-TEMPERATURE ELECTROLYSIS PROGRAM AT THE IDAHO NATIONAL LABORATORY: OBSERVATIONS ON PERFORMANCE DEGRADATION

    SciTech Connect

    J. E. O'Brien; C. M. Stoots; J. S. Herring; K. G. Condie; G. K. Housley

    2009-06-01

    This paper presents an overview of the high-temperature electrolysis research and development program at the Idaho National Laboratory, with selected observations of electrolysis cell degradation at the single-cell, small stack and large facility scales. The objective of the INL program is to address the technical and scale-up issues associated with the implementation of solid-oxide electrolysis cell technology for hydrogen production from steam. In the envisioned application, high-temperature electrolysis would be coupled to an advanced nuclear reactor for efficient large-scale non-fossil non-greenhouse-gas hydrogen production. The program supports a broad range of activities including small bench-scale experiments, larger scale technology demonstrations, detailed computational fluid dynamic modeling, and system modeling. A summary of the current status of these activities and future plans will be provided, with a focus on the problem of cell and stack degradation.

  8. The Adsorption and Desorption of Pb(2+) and Cd(2+) in Freeze-Thaw Treated Soils.

    PubMed

    Li, Linhui; Ma, Jincai; Xu, Meng; Li, Xu; Tao, Jiahui; Wang, Guanzhu; Yu, Jitong; Guo, Ping

    2016-01-01

    Adsorption and desorption are important processes that influence the potential toxicity and bioavailability of heavy metals in soils. However, information regarding adsorption and desorption behavior of heavy metals in soils subjected to freeze-thaw cycles is poorly understood. In the current study, the effect of freeze-thaw cycles with different freezing temperature (-15, -25, -35°C) on soil properties was investigated. Then the adsorption and desorption behavior of Pb(2+) and Cd(2+) in freeze-thaw treated soils was studied. The adsorption amounts of Pb(2+) and Cd(2+) in freeze-thaw treated soils were smaller than those in unfrozen soils (p < 0.05), due to the fact that pH, cation exchange capacity, organic matter content, free iron oxide content, and CaCO3 content in freeze-thaw treated soils were smaller than those in unfrozen soils. The adsorption amounts of Pb(2+) and Cd(2+) in soils treated with lower freezing temperatures were higher than those in soils treated with higher freezing temperatures. Desorption percentages of Pb(2+) and Cd(2+) in unfrozen soils were smaller than those in freeze-thaw treated soils (p < 0.05). The desorption percentages of Pb(2+) and Cd(2+) were smaller in soils treated with lower freezing temperatures than those in soils treated with higher freezing temperatures. The results obtained highlight the change of the adsorption and desorption behavior of typical heavy metals in freeze-thaw treated soils located in seasonal frozen soils zone in northeast China. PMID:26644028

  9. Thermal desorption of PCBs from contaminated soil with copper dichloride.

    PubMed

    Liu, Jie; Qi, Zhifu; Li, Xiaodong; Chen, Tong; Buekens, Alfons; Yan, Jianhua; Ni, Mingjiang

    2015-12-01

    Copper dichloride is an important catalyst both in the dechlorination of chlorinated aromatic compounds and the formation of PCDD/Fs. The effect of copper dichloride on polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) was studied in treated soil and off gas after thermal desorption of PCB-contaminated soil at 300, 400, 500, 600C. The presence of copper dichloride clearly enhances thermal desorption by promoting PCBs removal, destruction, and dechlorination. After thermal treatment at 600C for 1h, the removal efficiency and destruction efficiency for PCBs reached 98.1 and 93.9%, respectively. Compared with the positive influence on PCBs, copper dichloride catalyzed large amount of PCDFs formation at 300C, with the concentration ratio of 2.35. The effect of CuCl2 on PCDFs formation weakened with the rising temperature since PCDFs destruction became dominant under higher temperature. Different from PCDFs, PCDDs concentration in treated soil and off gas decreased continuously with the increasing temperature. PMID:26233752

  10. Thermal desorption treatability studies on selected mercury- and PCB-contaminated mixed waste

    SciTech Connect

    Krabill, R.H.; Shippy, J.L. III

    1996-12-31

    Thermal desorption (TD) is a process that has been targeted to remediate selected Department of Energy (DOE) hazardous/mixed waste soils and sludges by removing mercury, polychlorinated biphenyls (PCBs), and volatile organic contaminants to the satisfaction of the Land Disposal Restrictions (LDR) and the Federal Facilities Compliance Act (FFCA). It is a batch process in which waste solids are heated at a given temperature for a specified time to volatilize the contaminants, which are then separated from the radioactive components and collected for either immediate disposal or further treatment. This volatilization process depends on such variables as the solids temperature, residence time, and carrier gas flow. This paper discusses the effect of these parameters on the contaminant removal during TD. The experimental program demonstrates through scoping/engineering studies and verification/proof-of-principle studies that TD is the method of choice for the removal of these contaminants. The LDR treatment goal for high-mercury wastes is that the retorted residues exhibit a Toxicity Characteristic Leaching Procedure (TCLP) test result <0.02 ppm. However, the intent of this experimental program is to minimize the absolute quantity of mercury as well. The LDR treatment goal for PCBs is that the treated residue possess a concentration <2 ppm.

  11. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species.

    PubMed

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2015-12-21

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53-75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol at a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation. PMID:26696070

  12. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

    NASA Astrophysics Data System (ADS)

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2015-12-01

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53-75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol at a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.

  13. Adsorption-Desorption Kinetics of Soft Particles

    NASA Astrophysics Data System (ADS)

    Osberg, Brendan; Nuebler, Johannes; Gerland, Ulrich

    2015-08-01

    Adsorption-desorption processes are ubiquitous in physics, chemistry, and biology. Models usually assume hard particles, but within the realm of soft matter physics the adsorbing particles are compressible. A minimal 1D model reveals that softness fundamentally changes the kinetics: Below the desorption time scale, a logarithmic increase of the particle density replaces the usual Rnyi jamming plateau, and the subsequent relaxation to equilibrium can be nonmonotonic and much faster than for hard particles. These effects will impact the kinetics of self-assembly and reaction-diffusion processes.

  14. Clathrates: Computer programs to calculate fluid inclusion V- X properties using clathrate melting temperatures

    NASA Astrophysics Data System (ADS)

    Bakker, Ronald J.

    1997-02-01

    Knowledge of final clathrate melting temperatures is essential for estimates of salinity, bulk composition and density in H 2O-gas-rich fluid inclusions by nondestructive methods. The salinities calculated strongly depend on the thermodynamic model used, which involves many independent intensive properties and related parameters, such as osmotic coefficients, fugacity coefficients, gas solubilities. Four programs have been developed ( DENSITY, ICE, Q2, and NOSALT) using Turbo C++ version 3.0 to handle clathrate melting temperatures with several initiation procedures. These programs allow the calculation of bulk densities and compositions ( V- X properties) for H 2O-CO 2-CH 4-N 2-NaCl-KCl-CaCl 2-rich fluid inclusions using the clathrate melting temperature in combnation with liquidvapour equilibria, data from Raman spectroscopic analysis of the nonaqueous phases, and volume fraction estimates of the phases present. Calculations are restricted to fluid compositions less than eutectic salinities. If volume estimates are not provided, the programs calculate only the properties of the individual phases present in fluid inclusions during clathrate melting, including the salinity. Errors in measured parameters and in volume fraction estimates, which may be relatively large, are also handled by the programs.

  15. Atomic Layer Etching of Silicon by Thermal Desorption Method

    NASA Astrophysics Data System (ADS)

    Imai, Shigeru; Haga, Takeo; Matsuzaki, Osamu; Hattori, Takeo; Matsumura, Masakiyo

    1995-09-01

    Atomic layer etching of Si has been realized by modulating the substrate temperature synchronized with chlorine gas irradiation. This is based on the surface chemistry wherein chlorine atoms adsorbed on the clean Si surface at room temperature are thermally desorbed as SiCl2 over 650C. For Si(111) substrates, the etching rate R was saturated at about 3/7 monolayer per cycle for the peak temperature of more than 675C. The saturated etching rate corresponds to half the number of rest atoms of the Si(111) 7 7 surface. The chlorine dosage for the saturation was about 3.5 mTorr 4 s. The experimental results agreed well with the theoretical estimations based on the desorption kinetics of SiCl2. The increase of the surface roughness by etching was less than one monolayer.

  16. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

    DOE PAGESBeta

    Lillard, R. S.; Forsyth, R. T.

    2015-03-14

    The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared tomore » a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.« less

  17. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline ?-uranium

    SciTech Connect

    Lillard, R. S.; Forsyth, R. T.

    2015-03-14

    The kinetics of hydrogen desorption from polycrystalline ?-uranium (?-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline ?-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared to a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.

  18. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

    SciTech Connect

    Lillard, R. S.; Forsyth, R. T.

    2015-03-14

    The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared to a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.

  19. Dynamic gas temperature measurement system. Volume 2: Operation and program manual

    NASA Technical Reports Server (NTRS)

    Purpura, P. T.

    1983-01-01

    The hot section technology (HOST) dynamic gas temperature measurement system computer program acquires data from two type B thermocouples of different diameters. The analysis method determines the in situ value of an aerodynamic parameter T, containing the heat transfer coefficient from the transfer function of the two thermocouples. This aerodynamic parameter is used to compute a fequency response spectrum and compensate the dynamic portion of the signal of the smaller thermocouple. The calculations for the aerodynamic parameter and the data compensation technique are discussed. Compensated data are presented in either the time or frequency domain, time domain data as dynamic temperature vs time, or frequency domain data.

  20. Final report of comprehensive testing program for concrete at elevated temperatures

    SciTech Connect

    Oland, C.B.; Naus, D.J.; Robinson, G.C.

    1980-10-01

    The objective of this program was to define the variations in physical (thermal) and mechanical (strength) properties of limestone aggregate concrete and lightweight insulating concrete exposed to elevated temperatures that could occur as a result of a postulated large sodium spill in a lined LMFBR equipment cell. To meet this objective, five test series were conducted: (1) unconfined compression, (2) shear, (3) rebar bond, (4) sustained loading (creep), and (5) thermal properties. Mechanical property results are presented for concretes subjected to temperature up to 621{sup 0}C (1150{sup 0}F).

  1. Further development of the dynamic gas temperature measurement system. Volume 2: Computer program user's manual

    NASA Technical Reports Server (NTRS)

    Stocks, Dana R.

    1986-01-01

    The Dynamic Gas Temperature Measurement System compensation software accepts digitized data from two different diameter thermocouples and computes a compensated frequency response spectrum for one of the thermocouples. Detailed discussions of the physical system, analytical model, and computer software are presented in this volume and in Volume 1 of this report under Task 3. Computer program software restrictions and test cases are also presented. Compensated and uncompensated data may be presented in either the time or frequency domain. Time domain data are presented as instantaneous temperature vs time. Frequency domain data may be presented in several forms such as power spectral density vs frequency.

  2. High-temperature turbine technology program. Turbine subsystem design report: Low-Btu gas

    SciTech Connect

    Horner, M.W.

    1980-12-01

    The objective of the US Department of Energy High-Temperature Turbine Technology (DOE-HTTT) program is to bring to technology readiness a high-temperature (2600/sup 0/F to 3000/sup 0/F firing temperature) turbine within a 6- to 10-year duration, Phase II has addressed the performance of component design and technology testing in critical areas to confirm the design concepts identified in the earlier Phase I program. Based on the testing and support studies completed under Phase II, this report describes the updated turbine subsystem design for a coal-derived gas fuel (low-Btu gas) operation at 2600/sup 0/F turbine firing temperature. A commercial IGCC plant configuration would contain four gas turbines. These gas turbines utilize an existing axial flow compressor from the GE product line MS6001 machine. A complete description of the Primary Reference Design-Overall Plant Design Description has been developed and has been documented. Trends in overall plant performance improvement at higher pressure ratio and higher firing temperature are shown. It should be noted that the effect of pressure ratio on efficiency is significally enhanced at higher firing temperatures. It is shown that any improvement in overall plant thermal efficiency reflects about the same level of gain in Cost of Electricity (COE). The IGCC concepts are shown to be competitive in both performance and cost at current and near-term gas turbine firing temperatures of 1985/sup 0/F to 2100/sup 0/F. The savings that can be accumulated over a thirty-year plant life for a water-cooled gas turbine in an IGCC plant as compared to a state-of-the-art coal-fired steam plant are estimated. A total of $500 million over the life of a 1000 MW plant is projected. Also, this IGCC power plant has significant environmental advantages over equivalent coal-fired steam power plants.

  3. Indaziflam sorption-desorption in diverse soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Indaziflam is a new preemergence-herbicide active ingredient, classified as a member of the new chemical class “alkylazine”. There is no published information on its fate and behavior in soil. This study is aimed at characterizing the adsorption and desorption of indaziflam in soils with different p...

  4. Quantum theory of laser-stimulated desorption

    NASA Technical Reports Server (NTRS)

    Slutsky, M. S.; George, T. F.

    1978-01-01

    A quantum theory of laser-stimulated desorption (LSDE) is presented and critically analyzed. It is shown how LSDE depends on laser-pulse characteristics and surface-lattice dynamics. Predictions of the theory for a Debye model of the lattice dynamics are compared to recent experimental results.

  5. A microsystems enabled field desorption source.

    SciTech Connect

    Hertz, Kristin L.; Resnick, Paul James; Schwoebel, Paul R.; Holland, Christopher E.; Chichester, David L.

    2010-07-01

    Technologies that have been developed for microelectromechanical systems (MEMS) have been applied to the fabrication of field desorption arrays. These techniques include the use of thick films for enhanced dielectric stand-off, as well as an integrated gate electrode. The increased complexity of MEMS fabrication provides enhanced design flexibility over traditional methods.

  6. Determination of five booster biocides in seawater by stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Girldez, I; Chaguaceda, E; Bujalance, M; Morales, E

    2013-01-01

    Stir bar sorptive extraction (SBSE) and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS) have been optimized for the determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in seawater samples. The parameters affecting the desorption and absorption steps were investigated using 10 mL seawater samples. The optimised conditions consisted of an addition of 0.2 g mL(-1) KCl to the sample, which was extracted with 10mm length, 0.5mm film thickness stir bars coated with polydimethylsiloxane (PDMS), and stirred at 900 rpm for 90 min at room temperature (25 C) in a vial. Desorption was carried out at 280 C for 5 min under 50 mL min(-1) of helium flow in the splitless mode while maintaining a cryotrapping temperature of 20 C in the programmed-temperature vaporization (PTV) injector of the GC-MS system. Finally, the PTV injector was ramped to a temperature of 280 C and the analytes were separated in the GC and detected by MS using the selected-ion monitoring (SIM) mode. The detection limits of booster biocides were found to be in the range of 0.005-0.9 ?g L(-1). The regression coefficients were higher than 0.999 for all analytes. The average recovery was higher than 72% (R.S.D.: 7-15%). All these figures of merit were established running samples in triplicate. This simple, accurate, sensitive and selective analytical method may be used for the determination of trace amounts of booster biocides in water samples from marinas. PMID:23246091

  7. Programmed temperature gasification study. Final report, October 1, 1979-November 30, 1980

    SciTech Connect

    Spoon, M.J.; Gardner, M.P.; Starkovich, J.A.; Fein, H.L.; Apte, A.J.

    1980-11-30

    An experimental, modeling and conceptual engineering analysis study has been performed to assess the feasibility of TRW's Programmed Temperature Gasification (PTG) concept for carbonizing caking coals without severe agglomeration. The concept involves control of carbonizing heating rate to maintain metaplast concentration at a level equal to or slightly below that which causes agglomeration. The experimental studies required the contruction of a novel programmed temperature, elevated pressure, hot stage video microscope for observation of coal particle changes during heating. This system was used to develop a minimum-time heating schedule capable of carbonizing the coal at elevated pressures in the presence of hydrogen without severe agglomeration. Isothermal fixed heating rate data for a series of coals were subsequently used to calibrate and verify the mathematical model for the PTG process. These results showed good correlation between experimental data and mathematical predictions. Commercial application of the PTG concept to batch, moving bed and fluid bed processing schemes was then evaluated. Based on the calibrated model programmed temperature gasification of the coal without severe agglomeration could be carried out on a commercial batch reaction in 4 to 12 minutes. The next step in development of the PTG concept for commercial application would require testing on a bench scale (3-inch diameter) gasifier coupled with a full commercial assessment to determine size and cost of various gasification units.

  8. Thermal Desorption/GCMS Analysis of Astrobiologically Relevant Organic Materials

    NASA Technical Reports Server (NTRS)

    McDonald, Gene D.

    2001-01-01

    Several macromolecular organic materials, both biologically-derived (type II kerogen and humic acid) and abiotic in origin (Murchison insoluble organic material, cyanide polymer, and Titan tholin) were subjected to thermal desorption using a Chromatoprobe attachment on a Varian Saturn 2000 GCMS system. Each sample was heated sequentially at 100, 200, and 300 C to release volatile components. The evolved compounds were then separated on a Supelco EC-1 dimethylsilica GC column and detected by the Saturn 2000 ion trap mass spectrometer. The various types of macromolecular organic material subjected to thermal desorption produced distinctly different GCMS chromatograms at each temperature, containing fractions of both low and high chromatographic mobility. The relative amounts of detectable volatiles released at each temperature also differed, with type II kerogen and cyanide polymer containing the highest percentage of low-temperature components. In all the samples, the highest yield of released compounds occurred at 300 C. Only cyanide polymer evolved a homologous hydrocarbon series, suggesting that it is the only material among those examined that contains a truly polymeric structure. Pyrolysis/gas chromatography/mass spectrometry has been used extensively for analysis of terrestrial organic macromolecular materials, and was also part of the instrument package on the Viking landers. Thorough analysis by pyrolysis usually employs temperatures of 500 C or higher, which for in situ analyses can be problematic given spacecraft power and materials constraints. This study demonstrates that heating of organic materials of astrobiological relevance to temperatures as low as 200-300 C for short periods releases volatile components that can be analyzed by gas chromatography and mass spectrometry. Even in the absence of full pyrolysis, useful chemical information on samples can be obtained, and materials from different biological and abiological sources can be distinguished. The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

  9. Film growth, adsorption and desorption kinetics of indigo on SiO2

    PubMed Central

    Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

    2015-01-01

    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 des orption. 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. PMID:24832297

  10. Improved micromachined column design and fluidic interconnects for programmed high-temperature gas chromatography separations.

    PubMed

    Gaddes, David; Westland, Jessica; Dorman, Frank L; Tadigadapa, Srinivas

    2014-07-01

    This work focuses on the development and experimental evaluation of micromachined chromatographic columns for use in a commercial gas chromatography (GC) system. A vespel/graphite ferrule based compression sealing technique is presented using which leak-proof fluidic interconnection between the inlet tubing and the microchannel was achieved. This sealing technique enabled separation at temperatures up to 350°C on a μGC column. This paper reports the first high-temperature separations in microfabricated chromatographic columns at these temperatures. A 2m microfabricated column using a double Archimedean spiral design with a square cross-section of 100μm×100μm has been developed using silicon microfabrication techniques. The microfabricated column was benchmarked against a 2m 100μm diameter commercial column and the performance between the two columns was evaluated in tests performed under identical conditions. High temperature separations of simulated distillation (ASTM2887) and polycyclic aromatic hydrocarbons (EPA8310) were performed using the μGC column in temperature programmed mode. The demonstrated μGC column along with the high temperature fixture offers one more solution toward potentially realizing a portable μGC device for the detection of semi-volatile environmental pollutants and explosives without the thermal limitations reported to date with μGC columns using epoxy based interconnect technology. PMID:24866564

  11. QUANTUM-STATE RESOLVED PRODUCTS VIA VACUUM ULTRAVIOLET PHOTOSTIMULATED DESORPTION FROM GEOLOIC CALCITE

    EPA Science Inventory

    We report the results of a photostimulated desorption (PSD) study of neutral CO products from room temperature geologic calcite utilizing fluences <300 microJ/cm2 of 157-nm excimer laser radiation. At this wavelength, we are coincident with an intense absorption peak such that m...

  12. DEMONSTRATION BULLETIN: X*TRAX MODEL 200 THERMAL DESORPTION SYSTEMS - CHEMICAL WASTE MANAGEMENT, INC.

    EPA Science Inventory

    The X*TRAX Mode! 200 Thermal Desorption System developed by Chemical Waste Management, Inc. (CWM), is a low-temperature process designed to separate organic contaminants from soils, sludges, and other solid media. The X*TRAX Model 200 is fully transportable and consists of thre...

  13. Adduct formation and energy redistribution in UV and IR matrix-assisted laser desorption ionization

    NASA Astrophysics Data System (ADS)

    Vertes, Akos; Bencsura, Akos; Sadeghi, Mehrnoosh; Wu, Xiongwu

    2000-03-01

    Molecular dynamics calculations were carried out to follow the first 100 ps of the plume formation in matrix-assisted laser desorption ionization (MALDI). Two specific issues were addressed: the desorption of guest species in the form of matrix adducts and some distinctive features of infrared (IR) MALDI. Co-desorption of guest and matrix ions in the form of an adduct was studied using positive substance P ions surrounded by sinapinic acid anions. Upon laser heating the surface layers of the matrix underwent phase transition and the adduct was transferred into the gas phase without decomposition. IR-MALDI was studied using succinic acid as a matrix in combination with triglycine guest molecules. The IR laser induced desorption process was modeled by coupling the succinic acid O-H bond to an external 900 K heat bath. The energy redistribution within the matrix molecules themselves and the transfer between the matrix and guest molecules resulted in an increase of the system temperature. The kinetic temperature of the matrix reached plateau at approximately 670 K within a few ps. The temperature of the guest molecule increased on a slower time scale and during the calculation the values remained several hundred K below the O-H vibrational temperature. The liftoff velocity of the guest species (approximately 300 m/s) was similar to the values obtained in our previous calculations for different matrices and excitation methods.

  14. Status of the INL high-temperature electrolysis research program experimental and modeling

    SciTech Connect

    J. E. O'Brien; C. M. Stoots; M. G. McKellar; E. A. Harvego; K. G. Condie; G. K. Housley; J. S. Herring; J. J. Hartvigsen

    2009-04-01

    This paper provides a status update on the high-temperature electrolysis (HTE) research and development program at the Idaho National Laboratory (INL), with an overview of recent large-scale system modeling results and the status of the experimental program. System analysis results have been obtained using the commercial code UniSim, augmented with a custom high-temperature electrolyzer module. The process flow diagrams for the system simulations include an advanced nuclear reactor as a source of high-temperature process heat, a power cycle and a coupled steam electrolysis loop. Several reactor types and power cycles have been considered, over a range of reactor coolant outlet temperatures. In terms of experimental research, the INL has recently completed an Integrated Laboratory Scale (ILS) HTE test at the 15 kW level. The initial hydrogen production rate for the ILS test was in excess of 5000 liters per hour. Details of the ILS design and operation will be presented. Current small-scale experimental research is focused on improving the degradation characteristics of the electrolysis cells and stacks. Small-scale testing ranges from single cells to multiple-cell stacks. The INL is currently in the process of testing several state-of-the-art anode-supported cells and is working to broaden its relationship with industry in order to improve the long-term performance of the cells.

  15. Testing program for determining the mechanical properties of concrete to temperatures of 621/sup 0/C

    SciTech Connect

    Oland, C.B.; Naus, D.J.; Robinson, G.C.

    1980-01-01

    Concrete temperatures in a Liquid Metal Fast Breeder Reactor (LMFBR) in excess of normal code limits can result from postulated large sodium spills in equipment cells. Elevated temperature concrete property data which may have application for providing a basis for the design and evaluation of such postulated accident conditions is limited. Data thus needed to be developed commensurate with LMFBR plant applications for critical physical and mechanical concrete properties under prototypic thermal accident conditions. A test program was conducted to define the variations in physical and mechanical properties of a limestone aggregate concrete and a lightweight insulating concrete exposed to elevated temperatures. Five test series were conducted: unconfined compression, shear, rebar bond, sustained loading (creep), and thermal properties. Testing procedures for determining the mechanical properties of concrete from ambient to 621/sup 0/C (1150/sup 0/F) are described. Ther thermal properties tests are discussed in a separate paper which is also being presented at this conference.

  16. Adsorption and desorption of contaminants

    SciTech Connect

    Palumbo, A.V.; Strong-Gunderson, J.M.; DeFlaun, M.; Ensley, B.

    1994-02-01

    The microbial remediation of sites Contaminated with organics is well documented, however, there are some significant problems that remain to be solved in the areas of contaminants sorbed to soils and non-aqueous phase liquid (NAPL) contamination. Methods of in situ bioremediation techniques employ either the stimulation of indigenous populations by nutrient addition, or the addition of prepared bacterial cultures to the subsurface environment. Problems of contaminant sorption and NAPL`s are related in that both encompass reduced contaminant bioavailability. Non-aqueous phase liquids have been identified as a priority area for research in the In situ Program due to their presence at DOE sites and the lack of adequate technology to effectively treat this contamination. Bioremediation technologies developed as a result of this project are easily transferred to industry.

  17. Method of enhancing selective isotope desorption from metals

    DOEpatents

    Knize, R.J.; Cecchi, J.L.

    1983-07-26

    This invention relates generally to the field of gas desorption from metals; and, more particularly, to a method of enhancing the selective desorption of a particular isotope of a gas from metals. Enhanced selective desorption is especially useful in the operation of fusion devices.

  18. Interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Zacharia, Renju; Ulbricht, Hendrik; Hertel, Tobias

    2004-04-01

    We have studied the interaction of polyaromatic hydrocarbons (PAHs) with the basal plane of graphite using thermal desorption spectroscopy. Desorption kinetics of benzene, naphthalene, coronene, and ovalene at submonolayer coverages yield activation energies of 0.50 eV, 0.85 eV, 1.40 eV, and 2.1 eV, respectively. Benzene and naphthalene follow simple first order desorption kinetics while coronene and ovalene exhibit fractional order kinetics owing to the stability of two-dimensional adsorbate islands up to the desorption temperature. Preexponential frequency factors are found to be in the range 1014 1021 s-1 as obtained from both Falconer-Madix (isothermal desorption) analysis and Antoines fit to vapor pressure data. The resulting binding energy per carbon atom of the PAH is 525 meV and can be identified with the interlayer cohesive energy of graphite. The resulting cleavage energy of graphite is 615 meV/atom, which is considerably larger than previously reported experimental values.

  19. Adsorption, initial growth and desorption kinetics of p-quaterphenyl on polycrystalline gold surfaces

    NASA Astrophysics Data System (ADS)

    Mllegger, S.; Stranik, O.; Zojer, E.; Winkler, A.

    2004-01-01

    Thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS) have been applied to investigate the kinetics of adsorption, layer growth and desorption of p-quaterphenyl (P4P) on polycrystalline gold surfaces. Two different desorption peaks resulting from a monolayer (wetting layer) and a multilayer can be observed. The multilayer predominantly grows in form of a continuous film at 93 K, whereas at room temperature needle-like island growth is observed. A rearrangement (island formation) of the continuous multilayer takes place during heating prior to desorption. The influence of carbon on the adsorption/desorption kinetics of the monolayer has been studied in detail. On the clean surface some amount of adsorbed P4P dissociates and hydrogen is released at about 650 and 820 K, respectively. No dissociation of P4P takes place on the carbon-covered surface. The intact P4P molecules of the monolayer desorb in form of two broad peaks around 420 and 600 K, the multilayer desorbs with zero order above 350 K. Quantitative measurements with a quartz microbalance yield a mean thickness of 0.27 nm for the monolayer, suggesting that the P4P molecules are lying flat on the surface, for both the clean and the carbon-covered surface.

  20. Adsorption and desorption studies of lysozyme by Fe3O4-polymer nanocomposite via fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Koc, Kenan; Alveroglu, Esra

    2015-06-01

    The work have been undertaken in this study is to synthesis and characterize Fe3O4-polymer nanocomposites which are having different morphological properties. Also, investigation of the adsorption and desorption behaviour of lysozyme onto Fe3O4-polymer nanocomposites have been studied. Fe3O4 nanoparticles, synthesized by in situ in polyacrylamide hydrogels, show super-paramagnetic behaviour and saturation magnetization of composite material have been tuned by changing the hydrogel conformation. Adsorption and desorption studies of lysozyme were followed by using pure water at room temperature via fluorescence measurements. Fluorescence measurements showed that, the composite materials adsorbed lysozyme molecules less than 20 s and higher monomer concentration of composite materials cause faster adsorption. Besides, structure of lysozyme molecules were not changed during the adsorption and desorption. As a result Fe3O4-polymer nanocomposites could be used for drug delivery, protein separation and PAAm gels could be used for synthesis of magnetic composites with varying magnetic properties.

  1. Competitive Sorption and Desorption of Chlorinated Organic Solvents (DNAPLs) in Engineered Natural Organic Matter

    SciTech Connect

    Tang, Jixin; Weber, Walter J., Jr.

    2004-03-31

    The effects of artificially accelerated geochemical condensation and maturation of natural organic matter on the sorption and desorption of trichloroethylene (TCE) and tetrachloroethylene (PCE) were studied. The sorption and desorption of TCE in the presence and absence of the competing PCE and 1,2-dichlorobenzene (DCB) were also examined. A sphagnum peat comprising geologically young organic matter was artificially ''aged'' using superheated water, thus increasing the aromaticity and the degree of condensation of its associated organic matter. The sorption of all solutes tested were increased remarkably and their respective desorptions reduced, by the aged peat. The sorption capacities and isotherm nonlinearities of the peat for both TCE and PCE were found to increase as treatment temperature increased. In the competitive sorption studies, both PCE and DCB were found to depress TCE sorption, with PCE having greater effects than DCB, presumably because the molecular structure o f the former is more similar to that of TCE.

  2. Desorption Process of Hydrogen on Platinum (100 and 111) Surfaces Measured by an Electrochemical Method

    NASA Astrophysics Data System (ADS)

    Harada, Shûji

    1999-05-01

    Dynamical property of the desorption process of hydrogen on platinum (100 and 111) surfaces has been investigated by an electrochemical method.In the method, the desorption process of hydrogen has been measured by the recovery process of the electromotive force (EMF) after breaking the short circuit of H2 \\vert H+ electrolyte \\vert Pt single crystal cells.These recovery process and their temperature dependence have been analyzed by a random adsorpton site distribution model. The experimental result of Pt(100)-H system was in good agreement with the present model. An unusual result of Pt(111)-H system was interpreted by surface relaxation.From the above new analysis of the desorption process, the mean stay time of hydrogen on the Pt surface was evaluated.The activation energy of the process was obtained from their Arrhenius' analyses of the mean stay time, which was correspond to the adsorption energy of hydrogen.

  3. Optimizing the relationship between chromatographic efficiency and retention times in temperature-programmed gas chromatography.

    PubMed

    Mjøs, Svein A; Waktola, Habtewold D

    2015-09-01

    A methodology that can maximise the chromatographic efficiency that can be achieved within a defined time frame in temperature-programmed gas chromatography is described. The efficiency can be defined as the inverse of peak widths measured in retention index units. This parameter can be described by a model similar to the van Deemter equation, which is expanded to account for the effect of the temperature rate in addition to the effect of carrier gas velocity. The model of efficiency is found by response surface methodology, where the temperature rates and the carrier gas velocities are systematically varied in the experiments. A second model that accurately explains the retention time of the last eluting compound can be found from the same experiments, and optimal conditions are found by combining the two models. The methodology has been evaluated with four capillary columns and three carrier gases, using fatty acid methyl esters as analytes. All experiments showed that there is a fairly linear decrease in efficiency with increasing temperature rates. At any temperature rate, optimal velocity is only marginally higher than the velocity that maximises chromatographic efficiency, since the carrier gas velocity has a limited effect on the retention times. PMID:26105965

  4. Evaluation of GeO desorption behavior in the metal/GeO2/Ge structure and its improvement of the electrical characteristics

    NASA Astrophysics Data System (ADS)

    Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

    2010-06-01

    The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metal/GeO2/Ge capacitors fabricated by thermal oxidation has been investigated. In the metal/GeO2/Ge stack, two processes of GeO desorption at different sites and at different temperatures were observed by thermal desorption spectroscopy measurements. The electrical characteristics of as-oxidized metal/GeO2/Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO2/Ge interface during oxidation of Ge substrates. On the other hand, the electrical properties were drastically improved by a postmetallization annealing at low temperature resulting in a metal catalyzed GeO desorption from the top interface.

  5. Evaluation of GeO desorption behavior in the metalGeO(2)Ge structure and its improvement of the electrical characteristics.

    PubMed

    Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

    2010-06-15

    The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metalGeO(2)Ge capacitors fabricated by thermal oxidation has been investigated. In the metalGeO(2)Ge stack, two processes of GeO desorption at different sites and at different temperatures were observed by thermal desorption spectroscopy measurements. The electrical characteristics of as-oxidized metalGeO(2)Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO(2)Ge interface during oxidation of Ge substrates. On the other hand, the electrical properties were drastically improved by a postmetallization annealing at low temperature resulting in a metal catalyzed GeO desorption from the top interface. PMID:20644659

  6. Easy and Accurate Calculation of Programmed Temperature Gas Chromatographic Retention Times by Back-Calculation of Temperature and Hold-up Time Profiles

    PubMed Central

    Boswell, Paul G.; Carr, Peter W.; Cohen, Jerry D.; Hegeman, Adrian D.

    2012-01-01

    Linear retention indices are commonly used to identify compounds in programmed-temperature gas chromatography (GC), but they are unreliable unless the original experimental conditions used to measure them are stringently reproduced. However, differences in many experimental conditions may be properly taken into account by calculating programmed-temperature retention times of compounds from their measured isothermal retention vs. temperature relationships. We call this approach retention projection. Until now, retention projection has been impractical because it required very precise, meticulous measurement of the temperature vs. time and hold-up time vs. temperature profiles actually produced by a specific GC instrument to be accurate. Here we present a new, easy-to-use methodology to precisely measure those profiles: We spike a sample with 25 n-alkanes and use their measured, programmed-temperature retention times to precisely back-calculate what the instrument profiles must have been. Then, when we use those back-calculated profiles to project retention times of 63 chemically diverse compounds, we found that the projections are extremely accurate (e.g. to 0.9 s in a 40 min ramp). They remained accurate with different temperature programs, GC instruments, inlet pressures, flow rates, and with columns taken from different batches of stationary phase while the accuracy of retention indices became worse the more the experimental conditions were changed from the original ones used to measure them. We also developed new, open-source software (http://www.retentionprediction.org/gc) to demonstrate the system. PMID:23040964

  7. High-temperature turbine technology program hot-gas path development test. Part II. Testing

    SciTech Connect

    Horner, M.W.

    1982-03-01

    This topical report of the US Department of Energy High-Temperature Turbine Technology (DOE-HTTT) Phase II program presents the results of testing full-scale water-cooled first-stage and second-stage turbine nozzles at design temperature and pressure to verify that the designs are adequate for operation in a full-scale turbine environment. Low-cycle fatigue life of the nozzles was demonstrated by subjecting cascade assemblies to several hundred simulated startup/shutdown turbine cycles. This testing was accomplished in the Hot-Gas Path Development Test Stand (HGPDTS), which is capable of evaluating full-scale combustion and turbine nozzle components. A three-throat cascade of the first-stage turbine nozzle was successfully tested at a nozzle inlet gas temperature of 2630/sup 0/F and a nozzle inlet pressure of 11.3 atmospheres. In addition to steady-state operation at the design firing temperature, the nozzle cascade was exposed to a simulated startup/shutdown turbine cycle by varying the firing temperature. A total of 42 h at the design point and 617 thermal cycles were accumulated during the test periods. First-stage nozzle test results show that measured metal and coolant temperatures correspond well to the predicted design values. This nozzle design has been shown to be fully satisfactory for the application (2600/sup 0/F), with growth capability to 3000/sup 0/F firing temperature. A post-test metallurgical examination of sectioned portions of the tested nozzles shows a totally bonded structure, confirming the test results and attesting to the successful performance of water-cooled composite nozzle hardware.

  8. Temperature-programmed high-performance liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Godin, Jean-Philippe; Hopfgartner, Grard; Fay, Laurent

    2008-09-15

    The utility of liquid chromatography coupled to the isotope ratio mass spectrometry technique (LC-IRMS) has already been established through a variety of successful applications. However, the analytical constraint related to the use of aqueous mobile phases limits the LC separation mechanism. We report here a new strategy for high-precision (13)C isotopic analyses based on temperature-programmed LC-IRMS using aqueous mobile phases. Under these conditions, the isotopic precision and accuracy were studied. On one hand, experiments were carried out with phenolic acids using isothermal LC conditions at high temperature (170 degrees C); on the other hand, several experiments were performed by ramping the temperature, as conventionally used in a gas chromatography-based method with hydrosoluble fatty acids and pulses of CO 2 reference gas. In isothermal conditions at 170 degrees C, despite the increase of the CO 2 background, p-coumaric acid and its glucuronide conjugate gave reliable isotopic ratios compared to flow injection analysis-isotopic ratio mass spectrometry (FIA-IRMS) analyses (isotopic precision and accuracy are lower than 0.3 per thousand). On the opposite, for its sulfate conjugate, the isotopic accuracy is affected by its coelution with p-coumaric acid. Not surprisingly, this study also demonstrates that at high temperature (170 degrees C), a compound eluting with long residence time (i.e., ferulic acid) is degraded, affecting thus the delta (13)C (drift of 3 per thousand) and the peak area (compared to FIA-IRMS analysis at room temperature). Quantitation is also reported in isothermal conditions for p-coumaric acid in the range of 10-400 ng/mL and with benzoic acid as an internal standard. For temperature gradient LC-IRMS, in the area of the LC gradient (set up at 20 degrees C/min), the drift of the background observed produces a nonlinearity of SD (delta (13)C) approximately 0.01 per thousand/mV. To circumvent this drift, which impacts severely the precision and accuracy, an alternative approach, i.e., eluting the compound on the plateau of temperature studied was reported here. Other experiments with temperature-programmed LC-IRMS experiments are also reported with the presence of methanol in the injected solution to mimic residual solvent originating from the sample preparation or to slightly increase the solubility of the targeted compound for high-precision measurement. PMID:18690698

  9. The New Weather Radar for America's Space Program in Florida: A Temperature Profile Adaptive Scan Strategy

    NASA Technical Reports Server (NTRS)

    Carey, L. D.; Petersen, W. A.; Deierling, W.; Roeder, W. P.

    2009-01-01

    A new weather radar is being acquired for use in support of America s space program at Cape Canaveral Air Force Station, NASA Kennedy Space Center, and Patrick AFB on the east coast of central Florida. This new radar replaces the modified WSR-74C at Patrick AFB that has been in use since 1984. The new radar is a Radtec TDR 43-250, which has Doppler and dual polarization capability. A new fixed scan strategy was designed to best support the space program. The fixed scan strategy represents a complex compromise between many competing factors and relies on climatological heights of various temperatures that are important for improved lightning forecasting and evaluation of Lightning Launch Commit Criteria (LCC), which are the weather rules to avoid lightning strikes to in-flight rockets. The 0 C to -20 C layer is vital since most generation of electric charge occurs within it and so it is critical in evaluating Lightning LCC and in forecasting lightning. These are two of the most important duties of 45 WS. While the fixed scan strategy that covers most of the climatological variation of the 0 C to -20 C levels with high resolution ensures that these critical temperatures are well covered most of the time, it also means that on any particular day the radar is spending precious time scanning at angles covering less important heights. The goal of this project is to develop a user-friendly, Interactive Data Language (IDL) computer program that will automatically generate optimized radar scan strategies that adapt to user input of the temperature profile and other important parameters. By using only the required scan angles output by the temperature profile adaptive scan strategy program, faster update times for volume scans and/or collection of more samples per gate for better data quality is possible, while maintaining high resolution at the critical temperature levels. The temperature profile adaptive technique will also take into account earth curvature and refraction when geo-locating the radar beam (i.e., beam height and arc distance), including non-standard refraction based on the user-input temperature profile. In addition to temperature profile adaptivity, this paper will also summarize the other requirements for this scan strategy program such as detection of low-level boundaries, detection of anvil clouds, reducing the Cone Of Silence, and allowing for times when deep convective clouds will not occur. The adaptive technique will be carefully compared to and benchmarked against the new fixed scan strategy. Specific environmental scenarios in which the adaptive scan strategy is able to optimize and improve coverage and resolution at critical heights, scan time, and/or sample numbers relative to the fixed scan strategy will be presented.

  10. On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2014-01-07

    We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

  11. On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

    NASA Astrophysics Data System (ADS)

    Guo, Wei; Vlachos, Dionisios G.

    2014-01-01

    We model N2 desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N2 desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

  12. Sample Desorption/Onization From Mesoporous Silica

    SciTech Connect

    Iyer, Srinivas; Dattelbaum, Andrew M.

    2005-10-25

    Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

  13. Matrix effects in plasma desorption mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bouchonnet, Stephane; Hoppilliard, Yannik; Mauriac, Christine

    1993-07-01

    In Plasma Desorption (PD) Mass Spectrometry, valine/matrix mixtures have been studied in order to specify the influence of a matrix during the desorption-ionization (DI) of volume. The different matrices used were carboxylic acids (barbituric acid, 2-chloronicotinic acid, 3-chloropropionic acid, cysteine, pentafluorobenzoic acid, picric acid, sinapinic acid) and CsI, an inorganic salt. Three effects are proposed to explain the influence of each matrix on the DI of valine: a physical effect, a chemical effect and a (de)cationization effect. Thermodynamic diagrams are proposed to explain each effect. Each matrix gives either a specific effect or a superimposition of effects. The concentration effect of matrices is also studied.

  14. Plutonium sorption and desorption behavior on bentonite.

    PubMed

    Begg, James D; Zavarin, Mavrik; Tumey, Scott J; Kersting, Annie B

    2015-03-01

    Understanding plutonium (Pu) sorption to, and desorption from, mineral phases is key to understanding its subsurface transport. In this work we study Pu(IV) sorption to industrial grade FEBEX bentonite over the concentration range 10(-7)-10(-16) M to determine if sorption at typical environmental concentrations (?10(-12) M) is the same as sorption at Pu concentrations used in most laboratory experiments (10(-7)-10(-11) M). Pu(IV) sorption was broadly linear over the 10(-7)-10(-16) M concentration range during the 120 d experimental period; however, it took up to 100 d to reach sorption equilibrium. At concentrations ?10(-8) M, sorption was likely affected by additional Pu(IV) precipitation/polymerization reactions. The extent of sorption was similar to that previously reported for Pu(IV) sorption to SWy-1 Na-montmorillonite over a narrower range of Pu concentrations (10(-11)-10(-7) M). Sorption experiments with FEBEX bentonite and Pu(V) were also performed across a concentration range of 10(-11)-10(-7) M and over a 10 month period which allowed us to estimate the slow apparent rates of Pu(V) reduction on a smectite-rich clay. Finally, a flow cell experiment with Pu(IV) loaded on FEBEX bentonite demonstrated continued desorption of Pu over a 12 day flow period. Comparison with a desorption experiment performed with SWy-1 montmorillonite showed a strong similarity and suggested the importance of montorillonite phases in controlling Pu sorption/desorption reactions on FEBEX bentonite. PMID:25574607

  15. Effect of delivery condition on desorption rate of ZrCo metal hydride bed for fusion fuel cycle

    SciTech Connect

    Kang, H.G.; Yun, S.H.; Chung, D.; Oh, Y.H.; Chang, M.H.; Cho, S.; Chung, H.; Song, K.M.

    2015-03-15

    For the safety of fusion fuel cycle, hydrogen isotope gases including tritium are stored as metal hydride form. To satisfy fueling requirement of fusion machine, rapid delivery from metal hydride bed is one of major factors for the development of tritium storage and delivery system. Desorption from metal hydride depends on the operation scenario by pressure and temperature control of the bed. The effect of operation scenario and pump performance on desorption rate of metal hydride bed was experimentally investigated using ZrCo bed. The results showed that the condition of pre-heating scenario before actual delivery of gas affected the delivery performance. Different pumps were connected to desorption line from bed and the effect of pump capacity on desorption rate were also found to be significant. (authors)

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

    Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possibile 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.

  17. History of desorption induced by electronic transitions

    NASA Astrophysics Data System (ADS)

    Madey, Theodore E.

    1994-01-01

    Desorption induced by electronic transitions (DIET) encompasses electron- and photon-stimulated desorption (ESD and PSD) of atoms, molecules and ions from surfaces. In this paper, we focus on the key experimental and theoretical developments that have led to a fundamental understanding of DIET processes. We emphasize the effects of ionizing radiation, i.e., electrons and photons with energies ? 10 eV. The first DIET studies were occasioned mainly by the observation of anomalous peaks in mass spectrometers and spurious signals in ionization gauges. These observations were followed in the early 1960's by systematic studies of Redhead, and Menzel and Gomer, who independently proposed a Franck-Condon excitation model for electron-stimulated desorption of ions and neutrals from surfaces. In the years after this seminal work, ESD and PSD developed as fields of active interest to surface scientists. In addition to providing insights into the fundamental mechanisms linking atomic motion and electronic energy dissipation at surfaces, DIET investigations are continuing to impact upon radiation damage processes in areas as diverse as X-ray optics, semiconductor electronics, surface analysis and synthesis of molecules in interplanetary space.

  18. A 70-kyr sea surface temperature record off southern Chile (Ocean Drilling Program Site 1233)

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Lamy, F.; Hebbeln, D.

    2005-12-01

    We present the first high-resolution alkenone-derived sea surface temperature (SST) reconstruction in the southeast Pacific (Ocean Drilling Program Site 1233) covering the major part of the last glacial period and the Holocene. The record shows a clear millennial-scale pattern that is very similar to climate fluctuations observed in Antarctic ice cores, suggesting that the Southern Hemisphere high-latitude climate changes extended into the midlatitudes, involving simultaneous changes in air temperatures over Antarctica, sea ice extent, extension of the Antarctic Circumpolar Current, and westerly atmospheric circulation. A comparison to other midlatitude surface ocean records suggests that this "Antarctic" millennial-scale pattern was probably a hemisphere-wide phenomenon. In addition, we performed SST gradient reconstructions over the complete latitudinal range of the Pacific Eastern Boundary Current System for different time intervals during the last 70 kyr. The main results suggest an equatorward displaced subtropical gyre circulation during marine isotope stages 2 and 4.

  19. Lead Research and Development Activity for DOE's High Temperature, Low Relative Humidity Membrane Program (Topic 2)

    SciTech Connect

    James Fenton, PhD; Darlene Slattery, PhD; Nahid Mohajeri, PhD

    2012-09-05

    The Department of Energy’s High Temperature, Low Relative Humidity Membrane Program was begun in 2006 with the Florida Solar Energy Center (FSEC) as the lead organization. During the first three years of the program, FSEC was tasked with developing non-Nafion® proton exchange membranes with improved conductivity for fuel cells. Additionally, FSEC was responsible for developing protocols for the measurement of in-plane conductivity, providing conductivity measurements for the other funded teams, developing a method for through-plane conductivity and organizing and holding semiannual meetings of the High Temperature Membrane Working Group (HTMWG). The FSEC membrane research focused on the development of supported poly[perfluorosulfonic acid] (PFSA) – Teflon membranes and a hydrocarbon membrane, sulfonated poly(ether ether ketone). The fourth generation of the PFSA membrane (designated FSEC-4) came close to, but did not meet, the Go/No-Go milestone of 0.1 S/cm at 50% relative humidity at 120 °C. In-plane conductivity of membranes provided by the funded teams was measured and reported to the teams and DOE. Late in the third year of the program, DOE used this data and other factors to decide upon the teams to continue in the program. The teams that continued provided promising membranes to FSEC for development of membrane electrode assemblies (MEAs) that could be tested in an operating fuel cell. FSEC worked closely with each team to provide customized support. A logic flow chart was developed and discussed before MEA fabrication or any testing began. Of the five teams supported, by the end of the project, membranes from two of the teams were easily manufactured into MEAs and successfully characterized for performance. One of these teams exceeded performance targets, while the other requires further optimization. An additional team developed a membrane that shows great promise for significantly reducing membrane costs and increasing membrane lifetime.

  20. Thermodynamic study and methanothermal temperature-programmed reaction synthesis of molybdenum carbide

    NASA Astrophysics Data System (ADS)

    Roohi, Parham; Alizadeh, Reza; Fatehifar, Esmaeil

    2016-03-01

    Nanostructured molybdenum carbide (Mo2C) was successfully prepared from molybdenum trioxide (MoO3) using methanothermal temperature-programmed reaction. Thermodynamic analysis indicated that in presence of methane, the formation of Mo2C from MoO3 occurs through the path of MoO3 → MoO2 → Mo2C. The carburized MoO3 was characterized using X-ray diffraction (XRD), CHNS/O analysis, Brunauer-Emmett-Teller (BET) analysis, and field-emission scanning electron microscopy (FESEM). At final carburization temperatures of 700 and 800°C and at methane contents ranging from 5vol% to 20vol%, Mo2C was the only solid product observed in the XRD patterns. The results indicated that the effect of methane content on the formation of the carbide phase is substantial compared with the effect of carburization time. Elemental analysis showed that at a final temperature of 700°C, the carbon content of carburized MoO3 is very close to the theoretical carbon mass percentage in Mo2C. At higher carburization temperatures, excess carbon was deposited onto the surface of Mo2C. High-surface-area Mo2C was obtained at extremely low heating rates; this high-surface-area material is a potential electrocatalyst.

  1. Ambient pressure laser desorption and laser-induced acoustic desorption ion mobility spectrometry detection of explosives.

    PubMed

    Ehlert, Sven; Walte, Andreas; Zimmermann, Ralf

    2013-11-19

    The development of fast, mobile, and sensitive detection systems for security-relevant substances is of enormous importance. Because of the low vapor pressures of explosives and improvised explosive devices, adequate sampling procedures are crucial. Ion mobility spectrometers (IMSs) are fast and sensitive instruments that are used as detection systems for explosives. Ambient pressure laser desorption (APLD) and ambient pressure laser-induced acoustic desorption (AP-LIAD) are new tools suitable to evaporate explosives in order to detect them in the vapor phase. Indeed, the most important advantage of APLD or AP-LIAD is the capability to sample directly from the surface of interest without any transfer of the analyte to other surfaces such as wipe pads. A much more gentle desorption, compared to classical thermal-based desorption, is possible with laser-based desorption using very short laser pulses. With this approach the analyte molecules are evaporated in a very fast process, comparable to a shock wave. The thermal intake is reduced considerably. The functionality of APLD and AP-LIAD techniques combined with a hand-held IMS system is shown for a wide range of common explosives such as EGDN (ethylene glycol dinitrate), urea nitrate, PETN (pentaerythritol tetranitrate), HMTD (hexamethylene triperoxide diamine), RDX (hexogen), tetryl (2,4,6-trinitrophenylmethylnitramine), and TNT (trinitrotoluene). Detection limits down to the low nanogram range are obtained. The successful combination of IMS detection and APLD/AP-LIAD sampling is shown. PMID:24116702

  2. Sustainable remediation of mercury contaminated soils by thermal desorption.

    PubMed

    Sierra, María J; Millán, Rocio; López, Félix A; Alguacil, Francisco J; Cañadas, Inmaculada

    2016-03-01

    Mercury soil contamination is an important environmental problem that needs the development of sustainable and efficient decontamination strategies. This work is focused on the application of a remediation technique that maintains soil ecological and environmental services to the extent possible as well as search for alternative sustainable land uses. Controlled thermal desorption using a solar furnace at pilot scale was applied to different types of soils, stablishing the temperature necessary to assure the functionality of these soils and avoid the Hg exchange to the other environmental compartments. Soil mercury content evolution (total, soluble, and exchangeable) as temperature increases and induced changes in selected soil quality indicators are studied and assessed. On total Hg, the temperature at which it is reduced until acceptable levels depends on the intended soil use and on how restrictive are the regulations. For commercial, residential, or industrial uses, soil samples should be heated to temperatures higher than 280 °C, at which more than 80 % of the total Hg is released, reaching the established legal total Hg level and avoiding eventual risks derived from high available Hg concentrations. For agricultural use or soil natural preservation, conversely, maintenance of acceptable levels of soil quality limit heating temperatures, and additional treatments must be considered to reduce available Hg. Besides total Hg concentration in soils, available Hg should be considered to make final decisions on remediation treatments and potential future uses. Graphical Abstract Solar energy use for remediation of soils affected by mercury. PMID:26545893

  3. Trapping and desorption of complex organic molecules in water at 20 K

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

    2015-10-01

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

  4. Trapping and desorption of complex organic molecules in water at 20 K.

    PubMed

    Burke, Daren J; Puletti, Fabrizio; Woods, Paul M; Viti, Serena; Slater, Ben; Brown, Wendy A

    2015-10-28

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices. PMID:26520540

  5. Thermal desorption mass analysis of carbon fiber surfaces: surface oxygen complexes

    SciTech Connect

    Fagan, D.T.; Kuwana, T.

    1989-05-01

    A thermal desorption mass spectrometry (TDMS) system was constructed and applied to study the removal of adsorbed material and the decomposition of surface oxygen complexes from carbon fiber surfaces. The system consisted of a Balzers QMG 511 quadrupole mass spectrometer contained within a vacuum system employing separate chambers for analysis and adsorption. Carbon fiber samples were heated by direct resistive heating in a linear increase up to 1000/degree/C under high vacuum. An initial desorption of as-received pitch-based fibers produced a variety of carbon-, oxygen-, hydrogen-, and nitrogen-containing fragments, as well as traces of species apparently containing chlorine and sulfur. The initial degassing step served to clean the carbon fibers for subsequent oxidation of the carbon with oxygen to form surface oxygen complexes. Such fibers then subjected to TDMS yielded carbon monoxide, CO, and carbon dioxide, CO/sub 2/ as the major desorption products resulting from the decomposition of the surface carbon-oxygen complexes. The observation of multiple peaks in the desorption rate versus temperature profiles indicates that CO originates from possibly more than four different sites, and CO/sub 2/ from at least two sites. The number of sites and the quantity of CO or CO/sub 2/ produced at each site depended on the time and temperature of the prior oxidative treatment with oxygen. The activation energy for CO/sub 2/ generation from the oxidized carbon surface was determined to be 187 /plus minus/ 13 kJ/mol.

  6. A hot hole-programmed and low-temperature-formed SONOS flash memory

    PubMed Central

    2013-01-01

    In this study, a high-performance TixZrySizO flash memory is demonstrated using a solgel spin-coating method and formed under a low annealing temperature. The high-efficiency charge storage layer is formed by depositing a well-mixed solution of titanium tetrachloride, silicon tetrachloride, and zirconium tetrachloride, followed by 60 s of annealing at 600C. The flash memory exhibits a noteworthy hot hole trapping characteristic and excellent electrical properties regarding memory window, program/erase speeds, and charge retention. At only 6-V operation, the program/erase speeds can be as fast as 120:5.2 ?s with a 2-V shift, and the memory window can be up to 8 V. The retention times are extrapolated to 106 s with only 5% (at 85C) and 10% (at 125C) charge loss. The barrier height of the TixZrySizO film is demonstrated to be 1.15 eV for hole trapping, through the extraction of the Poole-Frenkel current. The excellent performance of the memory is attributed to high trapping sites of the low-temperature-annealed, high-? solgel film. PMID:23899050

  7. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    SciTech Connect

    Chunshan Song; Schobert, H.H.; Parfitt, D.P.

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  8. Laser desorption fast gas chromatography-mass spectrometry in supersonic molecular beams.

    PubMed

    Shahar, T; Dagan, S; Amirav, A

    1998-06-01

    A novel method for fast analysis is presented. It is based on laser desorption injection followed by fast gas chromatography-mass spectrometry (GC-MS) in supersonic molecular beams. The sample was placed in an open air or purged laser desorption compartment, held at atmospheric pressure and near room temperature conditions. Desorption was performed with a XeCl Excimer pulsed laser with pulse energy of typically 3 mJ on the surface. About 20 pulses at 50 Hz were applied for sample injection, resulting in about 0.4 s injection time and one or a few micrograms sample vapor or small particles. The laser desorbed sample was further thermally vaporized at a heated frit glass filter located at the fast GC inlet. Ultrafast GC separation and quantification was achieved with a 50-cm-long megabore column operated with a high carrier gas flow rate of up to 240 mL/min. The high carrier gas flow rate provided effective and efficient entrainment of the laser desorbed species in the sweeping gas. Following the fast GC separation, the sample was analyzed by mass spectrometry in supersonic molecular beams. Both electron ionization and hyperthermal surface ionization were employed for enhanced selectivity and sensitivity. Typical laser desorption analysis time was under 10 s. The laser desorption fast GC-MS was studied and demonstrated with the following sample/matrices combinations, all without sample preparation or extraction: (a) traces of dioctylphthalate plasticizer oil on stainless steel surface and the efficiency of its cleaning; (b) the detection of methylparathion and aldicarb pesticides on orange leaves; (c) water surface analysis for the presence of methylparathion pesticide; (d) caffeine analysis in regular and decaffeinated coffee powder; (e) paracetamol and codeine drug analysis in pain relieving drug tablets; (f) caffeine trace analysis in raw urine; (g) blood analysis for the presence of 1 ppm lidocaine drug. The features and advantages of the laser desorption fast GC-MS are demonstrated and discussed. PMID:9879375

  9. Estimation of the gelatinization temperature of noodles from water sorption curves under temperature-programmed heating conditions.

    PubMed

    Hasegawa, Ayako; Ogawa, Takenobu; Adachi, Shuji

    2012-01-01

    A novel method in which the water sorption curve is observed under linearly temperature-raising conditions was proposed to estimate the gelatinization temperature of starch-containing foods, it was applied in an estimation of the gelatinization temperatures of dried noodles. The gelatinization temperatures of two kinds of spaghetti, dried at high and low temperature, were 52.3 and 53.1 C, and those of udon, kishimen, juwari-soba, hachiwari-soba, so-called common soba, Malony(), and kuzukiri were 57.0, 57.8, 61.1, 59.6, 57.4, 48.4, and 49.1 C. The gelatinization temperatures estimated by the method were between the onset and peak temperatures obtained by differential scanning calorimetric measurement. PMID:23132576

  10. Sorption and desorption of cobalt by Oscillatoria anguistissima.

    PubMed

    Ahuja, P; Gupta, R; Saxena, R K

    1999-07-01

    Oscillatoria anguistissima rapidly adsorbs appreciable amounts of cobalt from the aqueous solutions within 15 min of initial contact with the metal solution. O. anguistissima showed a high sequestration of cobalt at low equilibrium concentrations, and it followed the Freundlich model of adsorption. The adsorption is a strongly pH-dependent and temperature-independent phenomenon. The presence of Mg2+ and Ca2+ (100-200 ppm) resulted in decline in Co2+ adsorption capacity of Oscillatoria biomass. Sulphate and nitrate (0. 75-10 mM) drastically reduced the extent of Co2+ biosorption. The biosorption of cobalt is an ion-exchange process as the Co2+ binding was accompanied by release of a large amounts of Mg2+ ions. Na2CO3 (1.0 mM) resulted in about 76% desorption of Co2+ from the loaded biomass. PMID:10387117

  11. In situ thermal desorption of soils impacted with chlorinated solvents

    SciTech Connect

    Vinegar, H.J.; Stegemeier, G.L.; Carl, F.G.; Stevenson, J.D.; Dudley, R.J.

    1999-07-01

    In situ thermal desorption (ISTD) has been demonstrated to remove high concentrations of chlorinated solvents such as PCE and TCE even from tight clay soils. ISTD applies heat and vacuum simultaneously to subsurface soils using thermal blankets for shallow contaminants (less than 2 ft depth) and thermal wells for deeper contamination. The ISTD process possesses a high removal efficiency because the narrow range of soil thermal conductivities provides excellent sweep efficiency and because its high operating temperature increases soil permeabilities and achieves complete displacement efficiency of contaminants in the gas phase. The first full scale commercial application of the ISTD well technology is described in detail for a site in Portland, Indiana, where silty clay soil was impacted with chlorinated solvents.

  12. Temperature-programmed technique accompanied with high-throughput methodology for rapidly searching the optimal operating temperature of MOX gas sensors.

    PubMed

    Zhang, Guozhu; Xie, Changsheng; Zhang, Shunping; Zhao, Jianwei; Lei, Tao; Zeng, Dawen

    2014-09-01

    A combinatorial high-throughput temperature-programmed method to obtain the optimal operating temperature (OOT) of gas sensor materials is demonstrated here for the first time. A material library consisting of SnO2, ZnO, WO3, and In2O3 sensor films was fabricated by screen printing. Temperature-dependent conductivity curves were obtained by scanning this gas sensor library from 300 to 700 K in different atmospheres (dry air, formaldehyde, carbon monoxide, nitrogen dioxide, toluene and ammonia), giving the OOT of each sensor formulation as a function of the carrier and analyte gases. A comparative study of the temperature-programmed method and a conventional method showed good agreement in measured OOT. PMID:25090138

  13. Gas absorption/desorption temperature-differential engine

    NASA Technical Reports Server (NTRS)

    Miller, C. G.

    1981-01-01

    Continuously operating compressor system converts 90 percent of gas-turbine plant energy to electricity. Conventional plants work in batch mode, operating at 40 percent efficiency. Compressor uses metal hydride matrix on outside of rotating drum to generate working gas, hydrogen. Rolling valve seals allow continuous work. During operation, gas is absorbed, releasing heat, and desorbed with heat gain. System conserves nuclear and fossil fuels, reducing powerplant capital and operating costs.

  14. Sorption/Desorption Interactions of Plutonium with Montmorillonite

    NASA Astrophysics Data System (ADS)

    Begg, J.; Zavarin, M.; Zhao, P.; Kersting, A. B.

    2012-12-01

    Plutonium (Pu) release to the environment through nuclear weapon development and the nuclear fuel cycle is an unfortunate legacy of the nuclear age. In part due to public health concerns over the risk of Pu contamination of drinking water, predicting the behavior of Pu in both surface and sub-surface water is a topic of continued interest. Typically it was assumed that Pu mobility in groundwater would be severely restricted, as laboratory adsorption studies commonly show that naturally occurring minerals can effectively remove plutonium from solution. However, evidence for the transport of Pu over significant distances at field sites highlights a relative lack of understanding of the fundamental processes controlling plutonium behavior in natural systems. At several field locations, enhanced mobility is due to Pu association with colloidal particles that serve to increase the transport of sorbed contaminants (Kersting et al., 1999; Santschi et al., 2002, Novikov et al., 2006). The ability for mineral colloids to transport Pu is in part controlled by its oxidation state and the rate of plutonium adsorption to, and desorption from, the mineral surface. Previously we have investigated the adsorption affinity of Pu for montmorillonite colloids, finding affinities to be similar over a wide range of Pu concentrations. In the present study we examine the stability of adsorbed Pu on the mineral surface. Pu(IV) at an initial concentration of 10-10 M was pre-equilibrated with montmorillonite in a background electrolyte at pH values of 4, 6 and 8. Following equilibration, aliquots of the suspensions were placed in a flow cell and Pu-free background electrolyte at the relevant pH was passed through the system. Flow rates were varied in order to investigate the kinetics of desorption and hence gain a mechanistic understanding of the desorption process. The flow cell experiments demonstrate that desorption of Pu from the montmorillonite surface cannot be modeled as a simple first order process. Furthermore, a pH dependence was observed, with less desorbed at pH 4 compared to pH 8. We suggest the pH dependence is likely controlled by reoxidation of Pu(IV) to Pu(V) and aqueous speciation. We will present models used to describe desorption behavior and discuss the implications for Pu transport. References: Kersting, A.B.; Efurd, D.W.; Finnegan, D.L.; Rokop, D.J.; Smith, D.K.; Thompson J.L. (1999) Migration of plutonium in groundwater at the Nevada Test Site, Nature, 397, 56-59. Novikov A.P.; Kalmykov, S.N.; Utsunomiya, S.; Ewing, R.C.; Horreard, F.; Merkulov, A.; Clark, S.B.; Tkachev, V.V.; Myasoedov, B.F. (2006) Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia, Science, 314, 638-641. Santschi, P.H.; Roberts, K.; Guo, L. (2002) The organic nature of colloidal actinides transported in surface water environments. Environ. Sci. Technol., 36, 3711-3719. This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. LLNL-ABS-570161

  15. Controlling Hydrogen Activation, Spillover, and Desorption with Pd-Au Single-Atom Alloys.

    PubMed

    Lucci, Felicia R; Darby, Matthew T; Mattera, Michael F G; Ivimey, Christopher J; Therrien, Andrew J; Michaelides, Angelos; Stamatakis, Michail; Sykes, E Charles H

    2016-02-01

    Key descriptors in hydrogenation catalysis are the nature of the active sites for H2 activation and the adsorption strength of H atoms to the surface. Using atomically resolved model systems of dilute Pd-Au surface alloys and density functional theory calculations, we determine key aspects of H2 activation, diffusion, and desorption. Pd monomers in a Au(111) surface catalyze the dissociative adsorption of H2 at temperatures as low as 85 K, a process previously expected to require contiguous Pd sites. H atoms preside at the Pd sites and desorb at temperatures significantly lower than those from pure Pd (175 versus 310 K). This facile H2 activation and weak adsorption of H atom intermediates are key requirements for active and selective hydrogenations. We also demonstrate weak adsorption of CO, a common catalyst poison, which is sufficient to force H atoms to spill over from Pd to Au sites, as evidenced by low-temperature H2 desorption. PMID:26747698

  16. Kinetics of hydrogen desorption from MgH2 and AlH3 hydrides

    NASA Astrophysics Data System (ADS)

    Terent'ev, P. B.; Gerasimov, E. G.; Mushnikov, N. V.; Uimin, M. A.; Maikov, V. V.; Gaviko, V. S.; Golovatenko, V. D.

    2015-12-01

    Kinetic parameters of the process of thermal decomposition of the MgH2 hydride (obtained by the method of the mechanoactivation of magnesium in a hydrogen atmosphere) and of the commercial AlH3 hydride have been studied upon the rapid heating in the range of temperatures of 150-510C at hydrogen pressures of 0-2 atm. The time dependences of the amount of hydrogen released by the metal hydrides at different temperatures and pressures have been determined. It has been shown that the activation energies of the hydrogen desorption are 135 kJ/mol for MgH2 and 107 kJ/mol for AlH3. The maximum rates of hydrogen desorption from the investigated metal hydrides have been established, and the temperatures and initial pressures that ensure the maximum rate and maximum volume of the hydrogen release have been determined.

  17. Statistical physics modeling of hydrogen desorption from LaNi4.75Fe0.25: Stereographic and energetic interpretations

    NASA Astrophysics Data System (ADS)

    Wjihi, Sarra; Dhaou, Houcine; Yahia, Manel Ben; Knani, Salah; Jemni, Abdelmajid; Lamine, Abdelmottaleb Ben

    2015-12-01

    Statistical physics treatment is used to study the desorption of hydrogen on LaNi4.75Fe0.25, in order to obtain new physicochemical interpretations at the molecular level. Experimental desorption isotherms of hydrogen on LaNi4.75Fe0.25 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? and n?, the receptor site densities N?M and N?M, and the energetic parameters P? and P?. The behaviors of these parameters are discussed in relationship with desorption process. A dynamic study of the ? and ? 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.

  18. MEASUREMENT OF VOCS DESORBED FROM BUILDING MATERIALS--A HIGH TEMPERATURE DYNAMIC CHAMBER METHOD

    EPA Science Inventory

    Mass balance is a commonly used approach for characterizing the source and sink behavior of building materials. Because the traditional sink test methods evaluate the adsorption and desorption of volatile organic compounds (VOC) at ambient temperatures, the desorption process is...

  19. Generation IV Reactors Integrated Materials Technology Program Plan: Focus on Very High Temperature Reactor Materials

    SciTech Connect

    Corwin, William R; Burchell, Timothy D; Katoh, Yutai; McGreevy, Timothy E; Nanstad, Randy K; Ren, Weiju; Snead, Lance Lewis; Wilson, Dane F

    2008-08-01

    Since 2002, the Department of Energy's (DOE's) Generation IV Nuclear Energy Systems (Gen IV) Program has addressed the research and development (R&D) necessary to support next-generation nuclear energy systems. The six most promising systems identified for next-generation nuclear energy are described within this roadmap. Two employ a thermal neutron spectrum with coolants and temperatures that enable hydrogen or electricity production with high efficiency (the Supercritical Water Reactor-SCWR and the Very High Temperature Reactor-VHTR). Three employ a fast neutron spectrum to enable more effective management of actinides through recycling of most components in the discharged fuel (the Gas-cooled Fast Reactor-GFR, the Lead-cooled Fast Reactor-LFR, and the Sodium-cooled Fast Reactor-SFR). The Molten Salt Reactor (MSR) employs a circulating liquid fuel mixture that offers considerable flexibility for recycling actinides and may provide an alternative to accelerator-driven systems. At the inception of DOE's Gen IV program, it was decided to significantly pursue five of the six concepts identified in the Gen IV roadmap to determine which of them was most appropriate to meet the needs of future U.S. nuclear power generation. In particular, evaluation of the highly efficient thermal SCWR and VHTR reactors was initiated primarily for energy production, and evaluation of the three fast reactor concepts, SFR, LFR, and GFR, was begun to assess viability for both energy production and their potential contribution to closing the fuel cycle. Within the Gen IV Program itself, only the VHTR class of reactors was selected for continued development. Hence, this document will address the multiple activities under the Gen IV program that contribute to the development of the VHTR. A few major technologies have been recognized by DOE as necessary to enable the deployment of the next generation of advanced nuclear reactors, including the development and qualification of the structural materials needed to ensure their safe and reliable operation. The focus of this document will be the overall range of DOE's structural materials research activities being conducted to support VHTR development. By far, the largest portion of material's R&D supporting VHTR development is that being performed directly as part of the Next-Generation Nuclear Plant (NGNP) Project. Supplementary VHTR materials R&D being performed in the DOE program, including university and international research programs and that being performed under direct contracts with the American Society for Mechanical Engineers (ASME) Boiler and Pressure Vessel Code, will also be described. Specific areas of high-priority materials research that will be needed to deploy the NGNP and provide a basis for subsequent VHTRs are described, including the following: (1) Graphite: (a) Extensive unirradiated materials characterization and assessment of irradiation effects on properties must be performed to qualify new grades of graphite for nuclear service, including thermo-physical and mechanical properties and their changes, statistical variations from billot-to-billot and lot-to-lot, creep, and especially, irradiation creep. (b) Predictive models, as well as codification of the requirements and design methods for graphite core supports, must be developed to provide a basis for licensing. (2) Ceramics: Both fibrous and load-bearing ceramics must be qualified for environmental and radiation service as insulating materials. (3) Ceramic Composites: Carbon-carbon and SiC-SiC composites must be qualified for specialized usage in selected high-temperature components, such as core stabilizers, control rods, and insulating covers and ducting. This will require development of component-specific designs and fabrication processes, materials characterization, assessment of environmental and irradiation effects, and establishment of codes and standards for materials testing and design requirements. (4) Pressure Vessel Steels: (a) Qualification of short-term, high-temperature properties of light water reactor steels for anticipated VHTR off-normal conditions must be determined, as well as the effects of aging on tensile, creep, and toughness properties, and on thermal emissivity. (b) Large-scale fabrication process for higher temperature alloys, such as 9Cr-1MoV, including ensuring thick-section and weldment integrity must be developed, as well as improved definitions of creep-fatigue and negligible creep behavior. (5) High-Temperature Alloys: (a) Qualification and codification of materials for the intermediate heat exchanger, such as Alloys 617 or 230, for long-term very high-temperature creep, creep-fatigue, and environmental aging degradation must be done, especially in thin sections for compact designs, for both base metal and weldments. (b) Constitutive models and an improved methodology for high-temperature design must be developed.

  20. Dendritic Aggregation of Oligothiophene During Desorption of 2,5-Diiodothiophene Multilayer and Topography-Induced Alignment of Oligothiophene Nanofibers

    SciTech Connect

    Liu,G.; Rider, K.; Nam, W.; Fonash, S.; Kim, S.

    2006-01-01

    The multilayer desorption behavior of 2,5-diidothiophene and the dendritic aggregation of photochemical reaction products during the desorption of 2,5-diiodothiophene multilayers have been studied. Like many other aromatic compounds, 2,5-diiodothiophene shows a multilayer desorption behavior different from the typical zeroth-order kinetics, a metastable desorption peak growth at {approx}220 K followed by a thick multilayer peak growth at {approx}235 K. Traditionally, these desorption behaviors have been attributed to the formation of three-dimensional clusters. This paper provides the direct evidence of this clustering process by producing nondesorbing photoreaction products in the multilayer and by imaging their clusters after the multilayer desorption. Oligothiophene species are produced via photochemical reactions of 2,5-diiodothiophene during the multilayer deposition at {approx}180 K in ultrahigh vacuum (UHV). Upon heating the multilayer to room temperature, the oligothiophene species forms into fibrous aggregates with a fractal dimension varying from 1.37 to 1.81 depending on their surface concentration. Using a topographical alteration of the substrate with a repeating pattern, these oligothiophene fibers can be aligned to a certain direction. This may allow in-situ fabrication of aligned conjugated polymer fibers directly on a target substrate.

  1. Low-Energy Photodesorption and Electron-Stimulated Desorption Mechanisms in Semiconductors.

    NASA Astrophysics Data System (ADS)

    Ekwelundu, Emmanuel Chikelue

    1988-12-01

    The aim of this research is to investigate low energy photodesorption and electron stimulated desorption mechanisms in semiconductors. Silicon, gallium arsenide and cadmium sulfide single crystals were used as representative semiconductors because their band gaps cut across both narrow and wide band gap semiconductors. Their clean surfaces were exposed to different doses of the following gases: O_2, NO, CO, CO_2 and SO_2 at room temperature but under different adsorption conditions. At low 10 ^{-10} torr pressure, the surfaces were irradiated with low energy (also low flux) photons and electrons. The desorbing species from the sample surfaces were monitored by a quadrupole mass spectrometer. CO, CO_2, NO, SO and SO _2 were observed to photodesorb when irradiated with photons. The desorption threshold energies were found to coincide with electron excitations from surface states within the band gap of the semiconductors to conduction band states; followed by thresholds corresponding to excitations across the direct gap. In GaAs and CdS, additional threshold could be traced to excitations from the high electron density of states within the valence band. The photodesorption signal at any wavelength greater than the threshold was found to be proportional to the incident photon flux, supporting a quantum mechanism for the observed photodesorption. The calculated quantum efficiency (yield) of 10^ {-5} to 10^{-4} molecules/photon is consistent with the value for semiconductors. CO^+, CO_2 ^+, C^+, O ^+, SO^+, S ^+, SO^+ and SO _2^+ were observed to desorb when the surfaces were irradiated with electrons in the energy range 0-200 eV. The desorption threshold energies were found to coincide approximately with electron excitations from the core levels of the semiconductors. From the core levels excited, it was possible to define in GaAs and CdS which of the desorbing species was bonded to which atom. The total desorption cross section for the desorbing species was found to be ~10 ^{-18} cm^2. A photodesorption mechanism was postulated for semiconductors which incorporated the photogeneration of holes in both the surface and valence band states, drift of the holes to the surface and the resultant annihilation of the surface localized bonds between the adsorbate and the semiconductor leading to desorption. For Electron Stimulated Desorption (ESD) from GaAs and CdS, our results could be explained using the Auger Stimulated Desorption (ASD) model. This is an extension of Knotek-Feibelman model to covalent and non-maximal valency systems. Our ESD results from silicon shows Menzel-Gomer -Redhead (MGR) and ASD models as the competitive desorption models.

  2. Activation energy of water desorption from guanosine.

    NASA Astrophysics Data System (ADS)

    Smith, Megan; Lee, Scott

    2008-10-01

    The interactions of the nucleic acids with their water of hydration are of fundamental importance and still imperfectly understood. As an initial effort, we have studied a component of RNA: the nucleoside guanosine (rG), composed of the ribose sugar and the guanine base. The interactions of the water of primary hydration with rG have been studied via thermogravimetric measurements and differential thermal analysis. These data yield the activation energy for the desorption of the water of primary hydration from rG.

  3. On the coverage dependence of Arrhenius parameters in thermal desorption of interacting adsorbates

    NASA Astrophysics Data System (ADS)

    Zuniga-Hansen, Nayeli; Silbert, Leonardo E.; Calbi, M. Mercedes

    2014-03-01

    In temperature programmed desorption (TPD) the ``compensation effect'' is a linear relationship between the activation energy, Ea, and the preexponential factor, ?n, of the Arrhenius equation. From the Arrhenius plot ln -?/? ? vs. 1/T, we can extract the activation energy and the preexponential factor to test the validity of linearity. A linear relationship has been demonstrated to be valid when the kinetic parameters are independent of the surface coverage. In the presence of adsorbate-adsorbate interactions this analysis fails because the second order effects come into play. The compensation effect arises from the assumption that the second order terms in the derivative of the plot sum to zero. Some authors refer to this as a ``forced'' compensation effect and show that it can yield misleading results. Therefore this effect has not been completely understood. We use kinetic Monte Carlo simulations on ordered and disordered surface configurations to investigate the coverage dependence of the kinetic parameters to verify whether the compensation effect provides reliable information for our system, we do this over a range of binding and interaction energies.

  4. Operable Unit 7-13/14 in situ thermal desorption treatability study work plan

    SciTech Connect

    Shaw, P.; Nickelson, D.; Hyde, R.

    1999-05-01

    This Work Plan provides technical details for conducting a treatability study that will evaluate the application of in situ thermal desorption (ISTD) to landfill waste at the Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL). ISTD is a form of thermally enhanced vapor vacuum extraction that heats contaminated soil and waste underground to raise its temperature and thereby vaporize and destroy most organics. An aboveground vapor vacuum collection and treatment system then destroys or absorbs the remaining organics and vents carbon dioxide and water to the atmosphere. The technology is a byproduct of an advanced oil-well thermal extraction program. The purpose of the ISTD treatability study is to fill performance-based data gaps relative to off-gas system performance, administrative feasibility, effects of the treatment on radioactive contaminants, worker safety during mobilization and demobilization, and effects of landfill type waste on the process (time to remediate, subsidence potential, underground fires, etc.). By performing this treatability study, uncertainties associated with ISTD as a selected remedy will be reduced, providing a better foundation of remedial recommendations and ultimate selection of remedial actions for the SDA.

  5. Thermal inactivation kinetics of Bacillus stearothermophilus spores using a linear temperature program.

    PubMed

    Leontidis, S; Fernndez, A; Rodrigo, C; Fernndez, P S; Magraner, L; Martnez, A

    1999-08-01

    A systematic study of the inactivation kinetics of Bacillus stearothermophilus spores was carried out in nonisothermic heating conditions using a linear temperature increase program and analyzing the experimental data by means of a one-step nonlinear regression. The D and z values estimated are close to those obtained in isothermic conditions and estimated by using a two-step model, first D values are calculated, and then in the second step a z value is deduced (D(121 degrees C) = 3.08 and 4.38 min, respectively, and z = 7 and 7.9 degrees C, respectively). No convergence problems were observed when using the one-step nonlinear regression proposed. The results indicated that the methodology applied in this study can be used to obtain kinetic data for bacterial spores, which could mean a significant reduction in the amount of experimental work employed to generate these data. PMID:10456754

  6. Field desorption of Na and Cs from graphene on iridium

    NASA Astrophysics Data System (ADS)

    Bernatskii, D. P.; Pavlov, V. G.

    2015-08-01

    Field electron and desorption microscopy has been used to study specific features of the field desorption of sodium and cesium ions adsorbed on the surface of iridium with graphene. It was found that adsorbed sodium atoms most strongly reduce the work function on graphene islands situated over densely packed faces of iridium. A strong electric field qualitatively similarly affects the sodium and cesium desorption processes from a field emitter to give two desorption phases and has no noticeable effect on the disintegration of the graphene layer.

  7. Synchronized Desorption Electrospray Ionization Mass Spectrometry Imaging.

    PubMed

    Comi, Troy J; Ryu, Seung Woo; Perry, Richard H

    2016-01-19

    Desorption electrospray ionization (DESI) has emerged as a powerful technique for mass spectral analysis and imaging under ambient conditions. Synchronization of DESI (sDESI) with the ion injection period (IT)of low-duty cycle mass spectrometers has been previously shown to improve sensitivity and reduce the amount of sample depleted during the acquisition of each spectrum (viz. MS scan time). In this report, we describe the development and characterization of an sDESI mass spectrometry imaging source (sDESI-MSI). Our results show that synchronization of DESI with the IT of an LTQ Orbitrap-XL mass spectrometer improves spatial resolution by factors of ?4-6. In addition, under certain experimental conditions, synchronization was essential to acquire distinct MS images of low-intensity endogenous FAs (< 5% relative intensity) in fingermarks at high sampling frequencies (step sizes ? 75 ?m). The magnitudes of these improvements in performance depend on the properties of the microdroplet spray, sample, and surface. Simulations that model analyte movement during desorption and the "washing effect" replicate the experimental results with the washing parameter having the greatest impact on performance. Thus, synchronization improves spatial resolution and sensitivity by decreasing the percentage of the total MS scan time that analytes are influenced by the "washing effect". Generally, synchronization of DESI with IT improves performance and expands the range of analytes, surfaces, and experimental conditions amenable to DESI-MSI, especially for analytes that are weakly attached to a surface. PMID:26569449

  8. Environment-dependent desorption of benzene molecules

    NASA Astrophysics Data System (ADS)

    Meserole, Chad A.; Vandeweert, Erno; Dou, Yusheng; Postawa, Zbigniew; Winograd, Nick

    2001-08-01

    We have investigated the dependence of the 8 keV Ar+ ion beam-induced desorption of neutral benzene (C6H6) molecules on the local environment. The probed system was comprised of carefully constructed combinations of C6H6 and sec-Butyl Alcohol (sBA) deposited on Ag(111). A pulsed 8 keV Ar+ ion beam at 45 incidence was used to stimulate the desorption of adsorbed molecules. Using state-selective resonant ionization spectroscopy and time-of-flight (TOF) mass spectrometry, C6H6 molecules in the ground state and in the first level of a vibrationally excited state were probed. TOF distributions were measured versus the exposure of the sBA. The results show that the ejection of the C6H6 depends strongly on both the internal energy and thickness of the formed layer. In general, as more sBA is added to the probed system, the TOF distributions tend to broaden and shift to higher times, and the relative C6H6 yields diminish rapidly. The vibrationally excited C6H6 is more sensitive to the addition of sBA, and an interpretation of the combined data suggests that the C6H6 desorbed in an excited state originates from the organic/vacuum interface.

  9. Laser Infrared Desorption Spectroscopy to Detect Complex Organic Molecules on Icy Planetary Surfaces

    NASA Technical Reports Server (NTRS)

    Sollit, Luke S.; Beegle, Luther W.

    2008-01-01

    Laser Desorption-Infrared Spectroscopy (LD-IR) uses an IR laser pulse to desorb surface materials while a spectrometer measures the emission spectrum of the desorbed materials (Figure 1). In this example, laser desorption operates by having the incident laser energy absorbed by near surface material (10 microns in depth). This desorption produces a plume that exists in an excited state at elevated temperatures. A natural analog for this phenomenon can be observed when comets approach the sun and become active and individual molecular emission spectra can be observed in the IR [1,2,3,4,5]. When this occurs in comets, the same species that initially emit radiation down to the ground state are free to absorb it, reducing the amount of detectable emission features. The nature of our technique results in absorption not occurring, because the laser pulse could easily be moved away form the initial desorption plume, and still have better spatial resolution then reflectance spectroscopy. In reflectance spectroscopy, trace components have a relatively weak signal when compared to the entire active nature of the surface. With LDIR, the emission spectrum is used to identify and analyze surface materials.

  10. Desorption of arsenic from exhaust activated carbons used for water purification.

    PubMed

    Di Natale, F; Erto, A; Lancia, A

    2013-09-15

    This work aims to the analysis of arsenic desorption from an exhaust activated carbon used for the purification of a natural water. This last was used to mimic the properties of common groundwater or drinking water. Different low-cost and harmless eluting solutions were considered, including distilled water, natural water, saline (NaCl, CaCl? and NaNO?) and basic (NaOH) solutions. Experimental results showed that, for 1g of activated carbon with arsenic loading close to the maximum value available for the model natural water (? ? 0.1 mg/g), it is possible to recover more than 80% of the arsenic using 20 ml of 0.1 M sodium chloride solution. A temperature variation within 20 and 40 C has scarce effect on desorption efficiency. A comparison between desorption data and adsorption isotherms data suggests that arsenic adsorption is actually a reversible process. Therefore, it is virtually possible to increase arsenic recovery efficiency close to 100% by increasing the NaCl concentration or the volume of the desorption solution, but a preliminary cost benefit analysis lead to consider a NaCl 0.1M solution as an optimal solution for practical applications. PMID:23811366

  11. CO2 adsorption-desorption performance of mesoporous zirconium hydroxide with robust water durability.

    PubMed

    Kamimura, Y; Endo, A

    2016-01-20

    The present study demonstrates for the first time, the development of mesoporous zirconium hydroxide with high CO2 capacity and sustainable adsorption-desorption performance within a broad range of pressures (100-3000 kPa). Mesoporous zirconium hydroxide with a high surface area of ?400 m(2) g(-1) was prepared by a simple and easy-to-handle precipitation route. The prepared high surface area mesoporous zirconium hydroxide exhibited significantly higher CO2 adsorption uptake and working adsorption capacity on a volumetric basis within a wide range of operating pressures of 100-3000 kPa than commercially available zeolite 13X. Reversible CO2 desorption was easily achieved by a pressure swing at moderate temperatures (298.15 K). Additionally, the prepared mesoporous zirconium hydroxide was adequately stable and strong to effectuate CO2 capture over multiple adsorption-desorption cycles without major reductions in its CO2 adsorption capacity. Furthermore, the effect of co-adsorbed water on the CO2 adsorption properties of mesoporous zirconium hydroxide was investigated. In the presence of co-adsorbed water, mesoporous zirconium hydroxide displayed reversible CO2 adsorption-desorption behavior in contrast to zeolite 13X that exhibited negligible CO2 adsorption within the wide range of pressures examined. The present study demonstrates the potential of high surface area mesoporous zirconium hydroxide toward efficient CO2 capturing processes. PMID:26726006

  12. Double DCO+ Rings Reveal CO Ice Desorption in the Outer Disk Around IM Lup

    NASA Astrophysics Data System (ADS)

    Öberg, Karin I.; Furuya, Kenji; Loomis, Ryan; Aikawa, Yuri; Andrews, Sean M.; Qi, Chunhua; van Dishoeck, Ewine F.; Wilner, David J.

    2015-09-01

    In a protoplanetary disk, a combination of thermal and non-thermal desorption processes regulate where volatiles are liberated from icy grain mantles into the gas phase. Non-thermal desorption should result in volatile-enriched gas in disk-regions where complete freeze-out is otherwise expected. We present Atacama Large Millimeter/Submillimeter Array observations of the disk around the young star IM Lup in 1.4 mm continuum, C18O 2-1, H13CO+ 3-2 and DCO+ 3-2 emission at ˜0.″5 resolution. The images of these dust and gas tracers are clearly resolved. The DCO+ line exhibits a striking pair of concentric rings of emission that peak at radii of ˜0.″6 and 2″ (˜90 and 300 AU, respectively). Based on disk chemistry model comparison, the inner DCO+ ring is associated with the balance of CO freeze-out and thermal desorption due to a radial decrease in disk temperature. The outer DCO+ ring is explained by non-thermal desorption of CO ice in the low-column-density outer disk, repopulating the disk midplane with cold CO gas. The CO gas then reacts with abundant H2D+ to form the observed DCO+ outer ring. These observations demonstrate that spatially resolved DCO+ emission can be used to trace otherwise hidden cold gas reservoirs in the outmost disk regions, opening a new window onto their chemistry and kinematics.

  13. Characterization of alkanethiol self-assembled monolayers on gold by thermal desorption spectroscopy.

    PubMed

    Stettner, Johanna; Winkler, Adolf

    2010-06-15

    SAM formation of undecanethiol (UDT) and mercaptoundecanoic acid (11-MUA) on Au(111) and on gold foils, using wet chemical preparation methods as well as physical vapor deposition (PVD) in UHV, has been studied by means of thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES). The main aim of this study was to explore the possible application of TDS to characterize the quality of a SAM and to determine its thermal stability. The influence of various parameters, like substrate pretreatment, film formation method, and type of the functional end group, has been studied in detail. Three different temperature regimes can be identified in TDS, which yields specific information about the organic layer: Desorption of disulfides around 400 K can be shown to result from standing molecules in a well-defined SAM. Desorption of intact molecules and of molecules with split-off sulfur is observed around 500 K, resulting from lying molecules. Finally, desorption of an appreciable amount of gold-containing molecules is observed around 700 K. This is more pronounced for 11-MUA than for UDT, and in addition more pronounced for solution-based SAMs than for PVD prepared SAMs. These results emphasize the important role of gold adatoms in SAM formation, as recently discussed in the literature. PMID:20345109

  14. Telecommunication system specific to high temperature environment for JAXA Mercury exploration program

    NASA Astrophysics Data System (ADS)

    Toda, Tomoaki; Kamata, Yukio; Kawahara, Kousuke; Maejima, Hironori; Hayakawa, Hajime

    2014-02-01

    BepiColombo is the joint Mercury exploration program between JAXA (Japan Aerospace Exploration Agency) and ESA (European Space Agency). MMO (Mercury Magnetospheric Orbiter) is JAXA's satellite in this program. She requires a telecommunication system that survives a harsh heat environment surrounding Mercury. She will stay in a polar orbit circulating Mercury for a year for continuous observations of Mercury magnetosphere. MMO has an X-band telecommunication system. We newly developed a high gain antenna for the use of her daily operations and wider field of view antennas for critical events. They are ones directly exposed to a high temperature environment of Mercury. The remains of the telecommunication system such as a transponder and a power amplifier were selected from the heritage of our past deep space missions. These instruments are placed inside MMO where a milder environment is expected than the outside. The total telecommunication system has been designed so that it should work through the MMO mission lifetime from the launch in 2016 to the end of the mission in 2025 including an extra year of extension. The system has experienced thermal environmental tests and proved its excellent resistivity to predicted environments. We will discuss these technologies incorporated in MMO and her telecommunication system design.

  15. Ultrahigh vacuum scanning tunneling microscopy nanofabrication and hydrogen/deuterium desorption from silicon surfaces: implications for complementary metal oxide semiconductor technology

    NASA Astrophysics Data System (ADS)

    Lyding, J. W.; Hess, K.; Abeln, G. C.; Thompson, D. S.; Moore, J. S.; Hersam, M. C.; Foley, E. T.; Lee, J.; Chen, Z.; Hwang, S. T.; Choi, H.; Avouris, Ph.; Kizilyalli, I. C.

    1998-06-01

    The development of ultrahigh vacuum-scanning tunneling microscopy (UHV-STM)-based nanofabrication capability for hydrogen passivated silicon surfaces has opened new opportunities for selective chemical processing, down to the atomic scale. The chemical contrast between clean and H-passivated Si(100) surfaces has been used to achieve nanoscale selective oxidation, nitridation, molecular functionalization, and metallization by thermal chemical vapor deposition (CVD). Further understanding of the hydrogen desorption mechanisms has been gained by extending the studies to deuterated surfaces. In these experiments, it was discovered that deuterium is nearly two orders of magnitude more difficult to desorb than hydrogen in the electronic desorption regime. This giant isotope effect provided the basis for an idea that has since led to the extension of complementary metal oxide semiconductor (CMOS) transistor lifetimes by factors of 10 or greater. Low temperature hydrogen and deuterium desorption experiments were performed to gain further insight into the underlying physical mechanisms. The desorption shows no temperature dependence in the high energy electronic desorption regime. However, in the low energy vibrational heating regime, hydrogen is over two orders of magnitude easier to desorb at 11 K than at room temperature. The enhanced desorption in the low temperature vibrational regime has enabled the quantification of a dramatic increase in the deuterium isotope effect at low voltages. These results may have direct implications for low voltage and/or low temperature scaled CMOS operation.

  16. The Effects of Moisture on LiD Single Crystals Studied by Temperature Programmed Reaction

    SciTech Connect

    Dinh, L.; Balooch, M.; Cecala, C.M.; Leckey, J.H.

    2000-09-14

    Temperature programmed reaction (TPR) technique was performed on LiOH powders and LiD single crystals previously exposed to different moisture levels. Our results show that the LiOH decomposition process has an activation energy barrier of 30 to 33.1 kcal/mol. The LiOH structure is stable even if kept at 320 K for 100 years. However, LiOH structures formed on the surface of LiD during moisture exposure at low dosages may have multiple activation energy barriers, some of which may be much lower than 30 kcal/mol. We attribute the lowering of the activation energy barrier for the LiOH decomposition to the existence of dangling bonds, cracks, and other long range disorders in the LiOH structures formed at low levels of moisture exposure. These defective LiOH structures may decompose significantly over the next 100 years of storage even at room temperature. At high moisture exposure levels, LiOH.H{sub 2}O formation is observed. The release of H{sub 2}O molecules from LiOH.H{sub 2}O structure has small activation energy barriers in the range of 13.8 kcal/mol to 16.0 kcal/mol. The loosely bonded H{sub 2}O molecules in the LiOH.H{sub 2}O structure can be easily pumped away at room temperature in a reasonable amount of time. Our experiments also suggest that handling LiD single crystals at an elevated temperature of 340 K or more reduces the growth rate of LiOH and LiOH.H{sub 2}O significantly. Therefore, a proposed way of minimizing hydrogen formation (due to H{sub 2}O reaction with LiD) in a closed system containing LiOH in the presence of LiD may be to handle LiD at a slightly, elevated temperature during the assembly.

  17. Temperature-programmed retention indices for gas chromatography-mass spectroscopy analysis of plant essential oils.

    PubMed

    Zhao, Chen-Xi; Liang, Yi-Zeng; Fang, Hong-Zhuang; Li, Xiao-Ning

    2005-11-25

    A total of 95 volatile compounds from the essential oil in buds of Syringa oblata Lindl (lilac) were identified by gas chromatography-mass spectrometry (GC-MS) combined with heuristic evolving latent projections (HELP) and moving subwindow searching (MSS). The identified compounds are mainly aliphatic, terpenes and aromatic compounds. Their temperature-programmed retention indices (PTRIs) on HP-5MS and DB-35MS at three heating rates of 2, 4 and 6 degrees C/min from 80 to 290 degrees C were obtained, which showed that aliphatic compounds give nearly constant PTRIs and PTRIs of terpenoids do not vary much at different heating rates. But PTRIs of aromatic compounds exhibit relatively large temperature dependence. PTRIs vary much more on DB-35MS than those on HP-5MS according to the compound types. In general, differences of PTRIs between the two columns increase from aliphatic compounds to terpenoids to polycyclic aromatic compounds. The PTRIs in different heating rates were used as cross-references in the identification of components in the essential oil. When they were used in analysis of essential oil from flowers of lilac, good results were obtained. These PTRIs would be a part of our PTRI database being constructed on components from plant essential oils. The results also showed that efficiency and reliability were improved greatly when chemometric method and PTRIs were used as assistants of GC-MS in identification of chemical components in plant essential oils. PMID:16289121

  18. High temperature experiments on a 4 tons UF6 container TENERIFE program

    SciTech Connect

    Casselman, C.; Duret, B.; Seiler, J.M.; Ringot, C.; Warniez, P.

    1991-12-31

    The paper presents an experimental program (called TENERIFE) whose aim is to investigate the behaviour of a cylinder containing UF{sub 6} when exposed to a high temperature fire for model validation. Taking into account the experiments performed in the past, the modelization needs further information in order to be able to predict the behaviour of a real size cylinder when engulfed in a 800{degrees}C fire, as specified in the regulation. The main unknowns are related to (1) the UF{sub 6} behaviour beyond the critical point, (2) the relationship between temperature field and internal pressure and (3) the equivalent conductivity of the solid UF{sub 6}. In order to investigate these phenomena in a representative way it is foreseen to perform experiments with a cylinder of real diameter, but reduced length, containing 4 tons of UF{sub 6}. This cylinder will be placed in an electrically heated furnace. A confinement vessel prevents any dispersion of UF{sub 6}. The heat flux delivered by the furnace will be calibrated by specific tests. The cylinder will be changed for each test.

  19. Oil spills debris clean up by thermal desorption.

    PubMed

    Araruna, J T; Portes, V L O; Soares, A P L; Silva, M G; Sthel, M S; Schramm, D U; Tibana, S; Vargas, H

    2004-07-01

    Oil spills represent a significant environmental issue in Brazil. This paper presents the latest results of a comprehensive experimental programme aimed at understanding how the presence of spilled oil affects the properties of sands and at studying alternatives to remediate the affected shores. Results indicate that oil causes a slight increase in grain size and uniformity, and oiled debris presents a smaller void ratio but a larger unit weight. It was also observed that effective strength parameters for both the natural and oiled debris were the same although the undrained strength of a natural sand is much higher than that of the contaminated sand. At ambient temperature, oiled debris emits methane and ammonia, and these emissions tend to increase with rising temperatures. On the other hand, the oil and grease content from oiled debris decreases with rising temperature and prolonged exposure. Finally, in situ thermal desorption seems to be a promising method for cleaning debris from oil spills. It is simple, fast and avoids all the difficulties associated with digging up the soil for disposal or cleanup. PMID:15177737

  20. MAGMIX: a basic program to calculate viscosities of interacting magmas of differing composition, temperature, and water content

    USGS Publications Warehouse

    Frost, T.P.; Lindsay, J.R.

    1988-01-01

    MAGMIX is a BASIC program designed to predict viscosities at thermal equilibrium of interacting magmas of differing compositions, initial temperatures, crystallinities, crystal sizes, and water content for any mixing proportion between end members. From the viscosities of the end members at thermal equilibrium, it is possible to predict the styles of magma interaction expected for different initial conditions. The program is designed for modeling the type of magma interaction between hypersthenenormative magmas at upper crustal conditions. Utilization of the program to model magma interaction at pressures higher than 200 MPa would require modification of the program to account for the effects of pressure on heat of fusion and magma density. ?? 1988.

  1. Sticking and desorption of hydrogen on graphite: A comparative study of different models

    PubMed Central

    Lepetit, Bruno; Lemoine, Didier; Medina, Zuleika; Jackson, Bret

    2011-01-01

    We study the physisorption of atomic hydrogen on graphitic surfaces with four different quantum mechanical methods: perturbation and effective Hamiltonian theories, close coupling wavepacket, and reduced density matrix propagation methods. Corrugation is included in the modeling of the surface. Sticking is a fast process which is well described by all methods. Sticking probabilities are of the order of a few percent in the collision energy range 025 meV, but are enhanced for collision energies close to those of diffraction resonances. Sticking also increases with surface temperature. Desorption is a slow process which involves multiphonon processes. We show, however, how to correct the close coupling wavepacket method to account for such phenomena and obtain correct time constants for initial state decay. Desorption time constants are in the range of 2050 ps for a surface temperature of 300 K. PMID:21428654

  2. Temperature

    NASA Technical Reports Server (NTRS)

    Berenson, P. J.; Robertson, W. G.

    1973-01-01

    The problems in human comfort in heat stress are emphasized, with less emphasis placed upon cold exposure problems. Physiological parameters related to human thermal interactions are discussed, as well as data concerning thermal protective clothing. The energy balance equation, heat transfer equation, thermal comfort, heat stress, and cold stress are also considered. A two node model of human temperature regulation in FORTRAN is appended.

  3. ATRAZINE DESORPTION KINETICS FROM A FRESH-WATER SEDIMENT

    EPA Science Inventory

    Research has shown that the sorption and desorption of neutral organic compounds to soils and sediments occurs in two stages, with an initial rapid sorption/desorption phase (usually less than an hour) followed by a slower phase that can last for several months to years for very ...

  4. Integrated field emission array for ion desorption

    DOEpatents

    Resnick, Paul J; Hertz, Kristin L; Holland, Christopher; Chichester, David; Schwoebel, Paul

    2013-09-17

    An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

  5. Desorption kinetics of small n-alkanes from magnesium oxide(100), platinum(111), and carbon(0001)/platinum(111) and studies of palladium nanoparticles: Growth and sintering on aluminum oxide(0001) and methane dissociation on magnesium oxide(100)

    NASA Astrophysics Data System (ADS)

    Tait, Steven L., Jr.

    Small alkane interactions with surfaces are of interest for a wide range of applications including catalysis, atmospheric chemistry, geochemistry and chemical sensing. We have investigated in fundamental detail the chemical physics underlying relevant elementary steps for heterogeneous catalysis by studying model surfaces that are well defined yet present the same local structure as on real industrial catalysts. We measured alkane desorption energy on MgO(100), Pt(111), and C(0001)/Pt(111) surfaces. The molecules, CNH2 N+2 (N = 1--4, 6, 8, 10), were each studied by temperature programmed desorption (TPD) over a range of initial coverages and heating rates. We developed a novel TPD analysis technique which allows for accurate determination of prefactors and coverage-dependent desorption energies. The prefactor for desorption was found to increase by several orders of magnitude with chain length. This increase can be physically justified by considering the increase in rotational entropy available to the molecules in the gas-like transition state for desorption. The desorption energy from each surface increased linearly with chain length with a small y-intercept. We also measured the dissociative sticking probability of methane on MgO-supported Pd nanoparticles and on Pd(111). On Pd(111), the sticking exhibits "normal energy scaling." We show that the Pd nanoparticle (3 nm wide) geometry must be decoupled from the measured sticking probabilities in order to compare the intrinsic reactivity of the Pd particles with Pd(111). We find that the sticking probability on 3 nm Pd particle surfaces is at most twice as large as on Pd(111). We have also examined the growth and sintering kinetics of Pd nanoparticles on alpha-Al2O3(0001) by non-contact atomic force microscopy and low-energy ion scattering spectroscopy. This is the first study of metal nanoparticles on a well-defined oxide surface where both of these techniques are used for characterization. The Pd grows initially as 2D islands at 300 K, with the transition to 3D particle growth at 0.25 monolayers. Upon heating at 1 K/s, the Pd particles (2.5 nm diameter for 0.8 monolayers at 300 K) sinters at a nearly constant rate, doubling in particle diameter by 1000 K.

  6. Modeling Organic Contaminant Desorption from Municipal Solid Waste Components

    NASA Astrophysics Data System (ADS)

    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 low plastics content, the model predicted that 50% of the initially sorbed toluene desorbed over a period of 5.8 days. In contrast, the model predicted that 50% of the initially sorbed toluene desorbed over a period of 4 years for the newer MSW mixture. These results suggest that toluene desorption rates from old MSW mixtures exceed methanogenic toluene degradation rates (toluene half-lives of about 30 to 100 days have been reported for methanogenic systems) and thus imply that biodegradation kinetics control the rate at which sorbed toluene is mineralized in old landfills. For newer MSW mixtures with a larger plastics content, toluene desorption rates are substantially slower; therefore, toluene desorption kinetics likely control the rate at which sorbed toluene can be mineralized in new landfills.

  7. FORTRAN program for calculating coolant flow and metal temperatures of a full-coverage-film-cooled vane or blade

    NASA Technical Reports Server (NTRS)

    Meitner, P. L.

    1978-01-01

    A computer program that calculates the coolant flow and the metal temperatures of a full-coverage-film-cooled vane or blade was developed. The analysis was based on compressible, one-dimensional fluid flow and on one-dimensional heat transfer and treats the vane or blade shell as a porous wall. The calculated temperatures are average values for the shell outer-surface area associated with each film-cooling hole row. A thermal-barrier coating may be specified on the shell outer surface, and centrifugal effects can be included for blade calculations. The program is written in FORTRAN 4 and is operational on a UNIVAC 1100/42 computer. The method of analysis, the program input, the program output, and two sample problems are provided.

  8. Photon stimulated desorption of neutral species from aluminum

    SciTech Connect

    Chou, T.S.

    1991-01-01

    Photon Simulated Desorption of neutral species (PSD) is the major dynamic gas load in electron synchrotron light source. In the National Synchrotron Light Source, PSD presented initial machine commissioning difficulty. Sensitivity to surface contamination on PSD had been experienced during an incident of Fomblin Oil contamination. U10B-Photon Stimulated Desorption Experimental Station is constructed to investigate: (1) the degree of the contribution to the photon stimulated desorption (PSD) from primary photon flux and scattered secondary photon flux, (2) the underlying mechanism for photon stimulated desorption, (3) criteria to chose the proper beam tube material for future a accelerator such as the Superconducting X-Ray Lithography Source (SXLS), Free Electron Laser (FEL), Superconducting Super Collider (SSC), Advanced Light Source (ALS) etc. In this report, only photon stimulated desorption of neutral species (PSD) from aluminum with different surface treatments is reported to show the great potential for this station to investigate beam tube material selection. 6 refs., 2 figs., 1 tab.

  9. Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

    PubMed Central

    Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M.

    2008-01-01

    We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

  10. High-Temperature Gas-Cooled Reactor Technology Development Program: Annual progress report for period ending December 31, 1987

    SciTech Connect

    Jones, J.E.,Jr.; Kasten, P.R.; Rittenhouse, P.L.; Sanders, J.P.

    1989-03-01

    The High-Temperature Gas-Cooled Reactor (HTGR) Program being carried out under the US Department of Energy (DOE) continues to emphasize the development of modular high-temperature gas-cooled reactors (MHTGRs) possessing a high degree of inherent safety. The emphasis at this time is to develop the preliminary design of the reference MHTGR and to develop the associated technology base and licensing infrastructure in support of future reactor deployment. A longer-term objective is to realize the full high-temperature potential of HTGRs in gas turbine and high-temperature, process-heat applications. This document summarizes the activities of the HTGR Technology Development Program for the period ending December 31, 1987.

  11. High-temperature gas-cooled reactor technology development program. Annual progress report for period ending December 31, 1982

    SciTech Connect

    Kasten, P.R.; Rittenhouse, P.L.; Bartine, D.E.; Sanders, J.P.

    1983-06-01

    During 1982 the High-Temperature Gas-Cooled Reactor (HTGR) Technology Program at Oak Ridge National Laboratory (ORNL) continued to develop experimental data required for the design and licensing of cogeneration HTGRs. The program involves fuels and materials development (including metals, graphite, ceramic, and concrete materials), HTGR chemistry studies, structural component development and testing, reactor physics and shielding studies, performance testing of the reactor core support structure, and HTGR application and evaluation studies.

  12. Thermal desorption of petroleum contaminants from soils and sand using a continuous feed lab scale rotary kiln

    SciTech Connect

    Chern, Hsien-Tsung S.; Bozzelli, J.W.

    1996-10-01

    A continuous feed rotary kiln was designed and constructed to study thermal desorption of petroleum hydrocarbon contaminants from soil and/or sand matrices. Desorption studies on sand were run on 1-dodecene, 1-hexadecene, naphthalene, and anthracene. Results show that desorption rates are effected most by temperature. Residence time is second in importance. Temperatures required for complete removal (98%) of the specific organics including multi ring aromatics range from 100-250{degrees}C. A matrix for optimized parameterization with a reasonable number of experiments was set up for studies on petroleum hydrocarbon contaminated soils from sites. Parameters included temperature, residence time, purge flow, kiln angle, rotation and soil feed. Parameters were varied to try and quantitate effects and determine optimum conditions. Temperature, residence time and purge gas velocity in this order were found to be the most important parameters in the desorption process. The effluent from the kiln was sampled and analyzed to determine the mass balance for carbon. Most of the carbon recovery ranged from 45-115%.

  13. Conceptual design for a full-scale VAC*TRAX vacuum thermal desorption unit. Final report, September 1992--December 1995

    SciTech Connect

    Palmer, C.R.

    1996-04-01

    Rust Federal Services is pleased to present this topical report on the results of our Phase II conceptual design work of the PRDA VAC*TRAX{sup SM} mobile vacuum thermal desorption technology demonstration program. Through the present Phase II conceptual design activities, Rust has developed an equipment design and permitting strategy that retains the flexibility of a mobile treatment system with the long term value and ease of access of a central facility. The process is designed to remove volatile matter from solid matrices by thermal desorption. The system is also designed with superior emission controls, making it an ideal system for the treatment of radioactive wastes.

  14. Research and development program for non-linear structural modeling with advanced time-temperature dependent constitutive relationships

    NASA Technical Reports Server (NTRS)

    Walker, K. P.

    1981-01-01

    Results of a 20-month research and development program for nonlinear structural modeling with advanced time-temperature constitutive relationships are reported. The program included: (1) the evaluation of a number of viscoplastic constitutive models in the published literature; (2) incorporation of three of the most appropriate constitutive models into the MARC nonlinear finite element program; (3) calibration of the three constitutive models against experimental data using Hastelloy-X material; and (4) application of the most appropriate constitutive model to a three dimensional finite element analysis of a cylindrical combustor liner louver test specimen to establish the capability of the viscoplastic model to predict component structural response.

  15. Time-dependent studies of metal retention to and desorption from nanoparticle aggregates

    NASA Astrophysics Data System (ADS)

    Kim, C. S.; Stegemeier, J. P.; Dale, J.; Gilbert, B.

    2008-12-01

    Nanoparticles play a potentially significant role in the mobility of aqueous metal species in a number of environmental systems through the sorption of metals onto their surfaces. Additionally, the natural and often rapid aggregation of nanosized particles in aqueous systems can lead to changes in their structure, available surface area, porosity, and reactivity that may modify the mechanisms and extents by which metal ions are retained. Such aggregation processes may subsequently facilitate the long-term sequestration of metals by inhibiting desorption from the nanoparticle aggregates, thus enhancing the removal of metals from solution into the solid phase. Real-time macroscopic adsorption/desorption batch experiments were conducted with synthetic iron oxyhydroxide nanoparticles to investigate changes in Cu(II) concentration under environmentally-relevant conditions. Nanoparticles were introduced into Cu(II)-bearing solutions as either monodispersed particles (initial size: ~5 nm) or multi-particle aggregates formed by increasing the pH, ionic strength, or temperature of the initial monodisperse suspensions. Ion-selective, conductivity, temperature and pH probes were used to track real time changes in the solution, specifically the uptake of Cu(II) and associated changes in pH and ionic strength. A desorption step was then performed by lowering the pH back below the macroscopic absorption edge previously determined for Cu(II) to the iron oxyhydroxide nanoparticles. Sufficient time was allowed after both the introduction of the nanoparticles and the desorption step for the system to reattain equilibrium. Results suggest that the various aggregation mechanisms influence the extent and timeframe of Cu(II) uptake and desorption differently depending on the degree of aggregation. Specifically, heating as a method of aggregation was the most effective at retaining metals in the solid phase and pH-based aggregation less so, while ionic strength-based aggregation had little effect relative to the monodisperse particles. These results agree with corresponding EXAFS studies of nanoparticle aggregates which indicate that the desorption step removes the weakly-held (i.e. surface-bound) metal fraction but retains strongly-held metals that appear to be more structurally incorporated within the nanoparticle aggregates. These findings have implications for the removal of hazardous metals from the aqueous phase and the design of remediation strategies targeting contaminated environments such as mine-impacted regions.

  16. Adsorption, desorption, and dissociation of benzene on TiO2(110) and Pd/TiO2(110) : Experimental characterization and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Zhou, J.; Dag, S.; Senanayake, S. D.; Hathorn, B. C.; Kalinin, S. V.; Meunier, V.; Mullins, D. R.; Overbury, S. H.; Baddorf, A. P.

    2006-09-01

    Adsorption and reaction of benzene molecules on clean TiO2(110) and on TiO2(110) with deposited Pd nanoparticles are investigated using a combination of scanning tunneling microscopy (STM), temperature-programmed desorption, and first-principles calculations. Above ˜50K , the one-dimensional motion of benzene between bridging oxygen rows is shown to be too fast for STM imaging. At 40K benzene molecules form chains on top of titanium rows, with calculations indicating every other benzene is rotated 30° . Both experimental and theoretical studies find no dissociative reactivity of benzene on the clean TiO2(110) surface, due to little hybridization between TiO2 and benzene electronic states. After deposition of Pd nanoparticles, molecular benzene is observed with STM both on the substrate and adjacent to metallic particles. Upon heating to 800K , benzene fully breaks down into its atomic constituents in a multistep decomposition process.

  17. Effect of partial exfoliation in carbon dioxide adsorption-desorption properties of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Tamilarasan, P.; Ramaprabhu, S.

    2014-09-01

    In this study, we have experimentally studied the effect of partial exfoliation in low-pressure (<100 kPa) carbon dioxide adsorption and desorption behavior of multiwalled carbon nanotubes (MWNTs). MWNTs were partially exfoliated by controlled oxidation followed by hydrogen assisted low temperature exfoliation method. The adsorption capacity of partially exfoliated MWNTs (PEMWNTs) is 3.4 times that of MWNTs. Adsorption-desorption isotherms of MWNTs are unique, which shows trapping behavior. The desorption behavior in association with isothermal adsorbate retention of MWNTs and PEMWNTs suggests possible CO2 trapping inside the tubes and at interstitials. It is found that the CO2 adsorbed PEMWNTs system has higher molecular orbital energy than CO2 adsorbed MWNTs system. Areal adsorption capacity analysis suggests the significant influence of surface functional groups on adsorption capacity. Adsorption isosteres of both adsorbents follow the Arrhenius relation stating the temperature dependent adsorption rate. The isosteric heats and change in entropy of adsorption have been determined at multiple adsorbed amounts from the corresponding adsorption isosteres.

  18. High-speed thermo-microscope for imaging thermal desorption phenomena.

    PubMed

    Staymates, Matthew; Gillen, Greg

    2012-07-01

    In this work, we describe a thermo-microscope imaging system that can be used to visualize atmospheric pressure thermal desorption phenomena at high heating rates and frame rates. This versatile and portable instrument is useful for studying events during rapid heating of organic particles on the microscopic scale. The system consists of a zoom lens coupled to a high-speed video camera that is focused on the surface of an aluminum nitride heating element. We leverage high-speed videography with oblique incidence microscopy along with forward and back-scattered illumination to capture vivid images of thermal desorption events during rapid heating of chemical compounds. In a typical experiment, particles of the material of interest are rapidly heated beyond their boiling point while the camera captures images at several thousand frames/s. A data acquisition system, along with an embedded thermocouple and infrared pyrometer are used to measure the temperature of the heater surface. We demonstrate that, while a typical thermocouple lacks the response time to accurately measure temperature ramps that approach 150 C/s, it is possible to calibrate the system by using a combination of infrared pyrometry, melting point standards, and a thermocouple. Several examples of high explosives undergoing rapid thermal desorption are also presented. PMID:22852730

  19. Enhanced desorption of persistent organic pollutants from microplastics under simulated physiological conditions.

    PubMed

    Bakir, Adil; Rowland, Steven J; Thompson, Richard C

    2014-02-01

    Microplastics have the potential to uptake and release persistent organic pollutants (POPs); however, subsequent transfer to marine organisms is poorly understood. Some models estimating transfer of sorbed contaminants to organisms neglect the role of gut surfactants under differing physiological conditions in the gut (varying pH and temperature), examined here. We investigated the potential for polyvinylchloride (PVC) and polyethylene (PE) to sorb and desorb (14)C-DDT, (14)C-phenanthrene (Phe), (14)C-perfluorooctanoic acid (PFOA) and (14)C-di-2-ethylhexyl phthalate (DEHP). Desorption rates of POPs were quantified in seawater and under simulated gut conditions. Influence of pH and temperature was examined in order to represent cold and warm blooded organisms. Desorption rates were faster with gut surfactant, with a further substantial increase under conditions simulating warm blooded organisms. Desorption under gut conditions could be up to 30 times greater than in seawater alone. Of the POP/plastic combinations examined Phe with PE gave the highest potential for transport to organisms. PMID:24212067

  20. Optical breathing of nano-porous antireflective coatings through adsorption and desorption of water

    PubMed Central

    Nielsen, Karsten H.; Kittel, Thomas; Wondraczek, Katrin; Wondraczek, Lothar

    2014-01-01

    We report on the direct consequences of reversible water adsorption on the optical performance of silica-based nanoporous antireflective (AR) coatings as they are applied on glass in photovoltaic and solar thermal energy conversion systems. In situ UV-VIS transmission spectroscopy and path length measurements through high-resolution interferometric microscopy were conducted on model films during exposure to different levels of humidity and temperature. We show that water adsorption in the pores of the film results in a notable increase of the effective refractive index of the coating. As a consequence, the AR effect is strongly reduced. The temperature regime in which the major part of the water can be driven-out rapidly lies in the range of 55C and 135C. Such thermal desorption was found to increase the overall transmission of a coated glass by ~ 1%-point. As the activation energy of isothermal desorption, we find a value of about 18?kJ/mol. Within the experimental range of our data, the sorption and desorption process is fully reversible, resulting in optical breathing of the film. Nanoporous AR films with closed pore structure or high hydrophobicity may be of advantage for maintaining AR performance under air exposure. PMID:25307536

  1. Gas adsorption and desorption in silica aerogels: a theoretical study of scattering properties.

    PubMed

    Detcheverry, F; Kierlik, E; Rosinberg, M L; Tarjus, G

    2006-04-01

    We present a numerical study of the structural correlations associated with gas adsorption and desorption in silica aerogels in order to provide a theoretical interpretation of scattering experiments. Following our earlier work, we use a coarse-grained lattice-gas description and determine the nonequilibrium behavior of the adsorbed gas within a local mean-field analysis. We focus on the differences between the adsorption and desorption mechanisms and their signature in the fluid-fluid and gel-fluid structure factors as a function of temperature. At low temperature, but still in the regime where the isotherms are continuous, we find that the adsorbed fluid density, during both filling and draining, is correlated over distances that may be much larger than the gel correlation length. In particular, extended fractal correlations may occur during desorption, indicating the existence of a ramified cluster of vapor filled cavities. This also induces an important increase of the scattering intensity at small wave vectors. The similarity and differences with the scattering of fluids in other porous solids such as Vycor are discussed. PMID:16711813

  2. High-speed thermo-microscope for imaging thermal desorption phenomena

    NASA Astrophysics Data System (ADS)

    Staymates, Matthew; Gillen, Greg

    2012-07-01

    In this work, we describe a thermo-microscope imaging system that can be used to visualize atmospheric pressure thermal desorption phenomena at high heating rates and frame rates. This versatile and portable instrument is useful for studying events during rapid heating of organic particles on the microscopic scale. The system consists of a zoom lens coupled to a high-speed video camera that is focused on the surface of an aluminum nitride heating element. We leverage high-speed videography with oblique incidence microscopy along with forward and back-scattered illumination to capture vivid images of thermal desorption events during rapid heating of chemical compounds. In a typical experiment, particles of the material of interest are rapidly heated beyond their boiling point while the camera captures images at several thousand frames/s. A data acquisition system, along with an embedded thermocouple and infrared pyrometer are used to measure the temperature of the heater surface. We demonstrate that, while a typical thermocouple lacks the response time to accurately measure temperature ramps that approach 150 C/s, it is possible to calibrate the system by using a combination of infrared pyrometry, melting point standards, and a thermocouple. Several examples of high explosives undergoing rapid thermal desorption are also presented.

  3. Testosterone sorption and desorption: effects of soil particle size.

    PubMed

    Qi, Yong; Zhang, Tian C; Ren, Yongzheng

    2014-08-30

    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. PMID:25108102

  4. Hydrogen Dissociation, Spillover, and Desorption from Cu-Supported Co Nanoparticles.

    PubMed

    Lewis, Emily A; Marcinkowski, Matthew D; Murphy, Colin J; Liriano, Melissa L; Sykes, E Charles H

    2014-10-01

    Co-Cu nanoparticles have recently been explored for Fischer-Tropsch synthesis (FTS) as a way to combine the long chain selectivity of Co with Cu's activity for alcohol formation in order to synthesize oxygenated transportation fuels. Depending on particle size, hydrogen dissociation can be a rate-determining step in cobalt-catalyzed FTS. To understand the fundamentals of uptake and release of hydrogen from the Co/Cu bimetallic system, we prepared well-defined Co nanoparticles on Cu(111). We demonstrate that hydrogen spills over from dissociation sites on the Co nanoparticles to the Cu(111) surface via the Co-Cu interface and that desorption of H occurs at a temperature that is lower than from Co or Cu alone, which we attribute to the Co-Cu interface sites. From this data, we have constructed an energy landscape for the facile dissociation, spillover, and desorption of hydrogen on the Co-Cu bimetallic system. PMID:26278448

  5. Effect of Titanium Doping of Al(111) Surfaces on Alane Formation Mobility, and Desorption

    SciTech Connect

    Chopra I. S.; Graetz J.; Chaudhuri, S.; Veyan, J.-F.; Chabal, Y. J.

    2011-07-05

    Alanes are critical intermediates in hydrogen storage reactions for mass transport during the formation of complex metal hydrides. Titanium has been shown to promote hydrogen desorption and hydrogenation, but its role as a catalyst is not clear. Combining surface infrared (IR) spectroscopy and density functional theory (DFT), the role of Ti is explored during the interaction of atomic hydrogen with Ti-doped Al(111) surfaces. Titanium is found to reduce the formation of large alanes, due to a decrease of hydrogen mobility and to trapping of small alanes on Ti sites, thus hindering oligomerization. For high doping levels ({approx}0.27 ML Ti) on Al(111), only chemisorbed AlH{sub 3} is observed on Ti sites, with no evidence for large alanes. Titanium also dramatically lowers the desorption temperature of large alanes from 290 to 190 K, due to a more restricted translational motion of these alanes.

  6. Continuous electron stimulated desorption using a ZrO2/Ag permeation membrane

    NASA Technical Reports Server (NTRS)

    Outlaw, R. A.; Hoflund, Gar B.; Davidson, M. R.

    1989-01-01

    During the development of an atomic oxygen beam generator for laboratory simulation of the atmospheric conditions in low earth orbit, a new technique for performing electron stimulated desorption (ESD) in a continuous manner has been developed. In this technique, oxygen permeates through an Ag membrane at elevated temperature thereby providing a continuous supply of oxygen atoms to the 1000-A ZrO2 coating at the vacuum interface. ESD then results in a large peak of neutral O2 molecules which ultimately decay into steady-state desorption. The ESD signal is linear with respect to primary beam flux (0.035 O2 molecules per electron at a primary beam energy of 1 keV) but nonlinear with respect to primary beam energy.

  7. Non-isothermal and isothermal hydrogen desorption kinetics of zirconium hydride

    NASA Astrophysics Data System (ADS)

    Ma, Mingwang; Xiang, Wei; Tang, Binghua; Liang, Li; Wang, Lei; Tan, Xiaohua

    2015-12-01

    Thermal desorption behaviors of zirconium hydride powder under non-isothermal and isothermal heat treatment conditions were studied using simultaneous TG-TDS. The phase transformation sequences were established by correlating the observed peaks of H2 release and mass loss. The origins of the peaks or shoulders in the TDS spectra were described as the equilibrium hydrogen pressures of a number of consecutive phase regions that decomposition reaction passed through. Effect of held temperature on the isothermal desorption behavior was taken into consideration, which was shown to be essential for the phase transformation sequence during ZrH2 decomposition. The zirconium monohydride ?ZrH was observed at ambient conditions, which has been supposed to be metastable for a long time.

  8. Computer program for afterheat temperature distribution for mobile nuclear power plant

    NASA Technical Reports Server (NTRS)

    Parker, W. G.; Vanbibber, L. E.

    1972-01-01

    ESATA computer program was developed to analyze thermal safety aspects of post-impacted mobile nuclear power plants. Program is written in FORTRAN 4 and designed for IBM 7094/7044 direct coupled system.

  9. Research and development program for the development of advanced time-temperature dependent constitutive relationships. Volume 1: Theoretical discussion

    NASA Technical Reports Server (NTRS)

    Cassenti, B. N.

    1983-01-01

    The results of a 10-month research and development program for the development of advanced time-temperature constitutive relationships are presented. The program included (1) the effect of rate of change of temperature, (2) the development of a term to include time independent effects, and (3) improvements in computational efficiency. It was shown that rate of change of temperature could have a substantial effect on the predicted material response. A modification to include time-independent effects, applicable to many viscoplastic constitutive theories, was shown to reduce to classical plasticity. The computation time can be reduced by a factor of two if self-adaptive integration is used when compared to an integration using ordinary forward differences. During the course of the investigation, it was demonstrated that the most important single factor affecting the theoretical accuracy was the choice of material parameters.

  10. Metastable helium atom stimulated desorption of H+ Ion

    PubMed

    Kurahashi; Yamauchi

    2000-05-15

    H+ desorption induced by the impact of metastable helium atoms has been found for H(2)O/Na/Ni(110) coadsorption systems. The measurements were carried out using a time-of-flight technique and a pulsed-discharge type metastable helium atom ( He(*)) source. It is concluded that the H+ desorption by He(*) is induced by a hole created on the valence levels via the Auger deexcitation of He(*). The H+ desorption by He(*) may be understood within the framework of the Menzel-Gomer-Readhead model. PMID:10990781

  11. Innovative site remediation technology: Thermal desorption. Volume 6

    SciTech Connect

    Anderson, W.C.

    1993-11-01

    The monograph on thermal desorption is one of a series of eight on innovative site and waste remediation technologies that are the culmination of a multiorganization effort involving more than 100 experts over a two-year period. The thermal desorption processes addressed in this monograph use heat, either direct or indirect, ex situ, as the principal means to physically separate and transfer contaminants from soils, sediments, sludges, filter cakes, or other media. Thermal desorption is part of a treatment train; some pre- and postprocessing is necessary.

  12. Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

    SciTech Connect

    Paxton, W. F. Howell, M.; Kang, W. P.; Davidson, J. L.; Brooks, M. M.; Tolk, N.

    2014-06-21

    The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classical processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.

  13. Salt Tolerance of Desorption Electrospray Ionization (DESI)

    SciTech Connect

    Jackson, Ayanna U.; Talaty, Nari; Cooks, R G; Van Berkel, Gary J

    2007-01-01

    Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.

  14. Electron stimulated desorption of atomic oxygen from silver

    NASA Technical Reports Server (NTRS)

    Outlaw, R. A.; Peregoy, W. K.; Hoflund, Gar B.; Corallo, Gregory R.

    1987-01-01

    The electron stimulated desorption (ESD) of neutral oxygen atoms from polycrystalline silver and of oxygen ions from Ag(110) has been studied. Polycrystalline Ag charged with (16)O2 and (18)O2 and bombarded by low-energy electrons (approx 100 eV) under ultrahigh vacuum (UHV) conditions emitted O atom flux levels of 1 x 10 to the 12th power/sq cm/s at a Ag temperature of 300 C. The flux was detected with a quadrupole mass spectrometer operating in the appearance potential mode. The neutral cross section at about 100 C was determined to be 7 x 10 to the -19 sq cm. Ancillary experiments conducted in a UHV chamber equipped with a cylindrical mirror analyzer and rigged for ion energy distribution and ion angular distribution were used to study O ions desorbed from Ag(110). Two primary O(+) energies of 2.4 and 5.4 eV were detected from the Ag(110) after having been dosed with 2500 L of (16)O2. It also appears that in both experiments there was strong evidence for directionality of the emitted flux. The results of this study serve as a proof of concept for the development of a laboratory atomic oxygen beam generator that simulates the gas flux environment experienced by orbiting vehicles.

  15. Mercury speciation during in situ thermal desorption in soil.

    PubMed

    Park, Chang Min; Katz, Lynn E; Liljestrand, Howard M

    2015-12-30

    Metallic mercury (Hg(0)) and its compounds are highly mobile and toxic environmental pollutants at trace level. In situ thermal desorption (ISTD) is one of the soil remediation processes applying heat and vacuum simultaneously. Knowledge of thermodynamic mercury speciation is imperative to understand the fate and transport of mercury during thermal remediation and operate the treatment processes in a cost-effective manner. Hence, speciation model for inorganic mercury was developed over a range of environmental conditions to identify distribution of dissolved mercury species and potential transformations of mercury at near source environment. Simulation of phase transitions for metallic mercury, mercury(II) chloride and mercury sulfide with temperature increase showed that complete vaporization of metallic mercury and mercury(II) chloride were achieved below the boiling point of water. The effect of soil compositions on mercury removal was also evaluated to better understand thermal remediation process. Higher vapor pressures expected both from soil pore water and inorganic carbonate minerals in soil as well as creation of permeability were significant for complete vaporization and removal of mercury. PMID:26275352

  16. Trace level detection of explosives in solution using leidenfrost phenomenon assisted thermal desorption ambient mass spectrometry.

    PubMed

    Saha, Subhrakanti; Mandal, Mridul Kanti; Chen, Lee Chuin; Ninomiya, Satoshi; Shida, Yasuo; Hiraoka, Kenzo

    2013-01-01

    The present paper demonstrates the detection of explosives in solution using thermal desorption technique at a temperature higher than Leidenfrost temperature of the solvent in combination with low temperature plasma (LTP) ionization. Leidenfrost temperature of a solvent is the temperature above which the solvent droplet starts levitation instead of splashing when placed on a hot metallic surface. During this desorption process, slow and gentle solvent evaporation takes place, which leads to the pre-concentration of less-volatile explosive molecules in the droplet and the explosive molecules are released at the last moment of droplet evaporation. The limits of detection for explosives studied by using this thermal desorption LTP ionization method varied in a range of 1 to 10 parts per billion (ppb) using a droplet volume of 20??L (absolute sample amount 90-630?fmol). As LTP ionization method was applied and ion-molecule reactions took place in ambient atmosphere, various ion-molecule adduct species like [M+NO2](-), [M+NO3](-), [M+HCO3](-), [M+HCO4](-) were generated together with [M-H](-) peak. Each peak was unambiguously identified using 'Exactive Orbitrap' mass spectrometer in negative ionization mode within 3?ppm deviation compared to its exact mass. This newly developed technique was successfully applied to detect four explosives contained in the pond water and soil sample with minor sample pre-treatment and the explosives were detected with ppb levels. The present method is simple, rapid and can detect trace levels of explosives with high specificity from solutions. PMID:24349927

  17. Trace Level Detection of Explosives in Solution Using Leidenfrost Phenomenon Assisted Thermal Desorption Ambient Mass Spectrometry

    PubMed Central

    Saha, Subhrakanti; Mandal, Mridul Kanti; Chen, Lee Chuin; Ninomiya, Satoshi; Shida, Yasuo; Hiraoka, Kenzo

    2013-01-01

    The present paper demonstrates the detection of explosives in solution using thermal desorption technique at a temperature higher than Leidenfrost temperature of the solvent in combination with low temperature plasma (LTP) ionization. Leidenfrost temperature of a solvent is the temperature above which the solvent droplet starts levitation instead of splashing when placed on a hot metallic surface. During this desorption process, slow and gentle solvent evaporation takes place, which leads to the pre-concentration of less-volatile explosive molecules in the droplet and the explosive molecules are released at the last moment of droplet evaporation. The limits of detection for explosives studied by using this thermal desorption LTP ionization method varied in a range of 1 to 10 parts per billion (ppb) using a droplet volume of 20 μL (absolute sample amount 90–630 fmol). As LTP ionization method was applied and ion–molecule reactions took place in ambient atmosphere, various ion–molecule adduct species like [M+NO2]−, [M+NO3]−, [M+HCO3]−, [M+HCO4]− were generated together with [M−H]− peak. Each peak was unambiguously identified using ‘Exactive Orbitrap’ mass spectrometer in negative ionization mode within 3 ppm deviation compared to its exact mass. This newly developed technique was successfully applied to detect four explosives contained in the pond water and soil sample with minor sample pre-treatment and the explosives were detected with ppb levels. The present method is simple, rapid and can detect trace levels of explosives with high specificity from solutions. PMID:24349927

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

    NASA Technical Reports Server (NTRS)

    Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

    1998-01-01

    Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

  20. TREATMENT OF HAZARDOUS PETROLEUM CONTAMINATED SOILS BY THERMAL DESORPTION TECHNOLOGIES

    EPA Science Inventory

    Spills, leaks, and accidental discharges of petroleum products have contaminated soil at thousands of sites in the United States. ne remedial action technique for treating petroleum contaminated soil is the use of thermal desorption technologies. his paper describes key elements ...

  1. Comparative sorption, desorption and leaching potential of aminocyclopyrachlor and picloram

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aminocyclopyrachlor and picloram sorption, desorption and leaching potential were investigated in three soils from Minnesota and Hawaii. Aminocyclopyrachlor and picloram sorption fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram ...

  2. Molecular beam-thermal hydrogen desorption from palladium

    SciTech Connect

    Lobo, R. F. M.; Berardo, F. M. V.; Ribeiro, J. H. F.

    2010-04-15

    Among the most efficient techniques for hydrogen desorption monitoring, thermal desorption mass spectrometry is a very sensitive one, but in certain cases can give rise to uptake misleading results due to residual hydrogen partial pressure background variations. In this work one develops a novel thermal desorption variant based on the effusive molecular beam technique that represents a significant improvement in the accurate determination of hydrogen mass absorbed on a solid sample. The enhancement in the signal-to-noise ratio for trace hydrogen is on the order of 20%, and no previous calibration with a chemical standard is required. The kinetic information obtained from the hydrogen desorption mass spectra (at a constant heating rate of 1 deg. C/min) accounts for the consistency of the technique.

  3. High-temperature performance prediction of iron ore fines and the ore-blending programming problem in sintering

    NASA Astrophysics Data System (ADS)

    Yan, Bing-ji; Zhang, Jian-liang; Guo, Hong-wei; Chen, Ling-kun; Li, Wei

    2014-08-01

    The high-temperature performance of iron ore fines is an important factor in optimizing ore blending in sintering. However, the application of linear regression analysis and the linear combination method in most other studies always leads to a large deviation from the desired results. In this study, the fuzzy membership functions of the assimilation ability temperature and the liquid fluidity were proposed based on the fuzzy mathematics theory to construct a model for predicting the high-temperature performance of mixed iron ore. Comparisons of the prediction model and experimental results were presented. The results illustrate that the prediction model is more accurate and effective than previously developed models. In addition, fuzzy constraints for the high-temperature performance of iron ore in this research make the results of ore blending more comparable. A solution for the quantitative calculation as well as the programming of fuzzy constraints is also introduced.

  4. Measurements on Ion-beam Loss Induced Desorption at GSI

    SciTech Connect

    Kollmus, H.; Bender, M.; Bellachioma, M.C.; Kraemer, A.; Reich-Sprenger, H.; Mahner, E.; Westerberg, L.; Hedlund, E.; Malyshev, O.B.

    2005-06-08

    Ion-beam loss induced desorption is a well known intensity limitation for low charge state heavy ion accelerators. Therefore dedicated measurements were performed, e.g., at CERN and at GSI in the last few years. In this work we will summarize results obtained at GSI with a focus on a observed scaling of the desorption yield with the electronic energy loss of the incident ion in the target material.

  5. Uranium and Neptunium Desorption from Yucca Mountain Alluvium

    SciTech Connect

    C.D. Scism; P.W. Reimus; M. Ding; S.J. Chipera

    2006-03-16

    Uranium and neptunium were used as reactive tracers in long-term laboratory desorption studies using saturated alluvium collected from south of Yucca Mountain, Nevada. The objective of these long-term experiments is to make detailed observations of the desorption behavior of uranium and neptunium to provide Yucca Mountain with technical bases for a more realistic and potentially less conservative approach to predicting the transport of adsorbing radionuclides in the saturated alluvium. This paper describes several long-term desorption experiments using a flow-through experimental method and groundwater and alluvium obtained from boreholes along a potential groundwater flow path from the proposed repository site. In the long term desorption experiments, the percentages of uranium and neptunium sorbed as a function of time after different durations of sorption was determined. In addition, the desorbed activity as a function of time was fit using a multi-site, multi-rate model to demonstrate that different desorption rate constants ranging over several orders of magnitude exist for the desorption of uranium from Yucca Mountain saturated alluvium. This information will be used to support the development of a conceptual model that ultimately results in effective K{sub d} values much larger than those currently in use for predicting radionuclide transport at Yucca Mountain.

  6. FORTRAN 77 programs for conductive cooling of dikes with temperature-dependent thermal properties and heat of crystallization

    USGS Publications Warehouse

    Delaney, P.T.

    1988-01-01

    Temperature histories obtained from transient heat-conduction theory are applicable to most dikes despite potential complicating effects related to magma flow during emplacement, groundwater circulation, and metamorphic reaction during cooling. Here. machine-independent FORTRAN 77 programs are presented to calculate temperatures in and around dikes as they cool conductively. Analytical solutions can treat thermal-property contrasts between the dike and host rocks, but cannot address the release of magmatic heat of crystallization after the early stages of cooling or the appreciable temperature dependence of thermal conductivity and diffusivity displayed by most rock types. Numerical solutions can incorporate these additional factors. The heat of crystallization can raise the initial temperature at the dike contact, ??c1, about 100??C above that which would be estimated if it were neglected, and can decrease the rate at which the front of solidified magma moves to the dike center by a factor of as much as three. Thermal conductivity and diffusivity of rocks increase with decreasing temperature and, at low temperatures, these properties increase more if the rocks are saturated with water. Models that treat these temperature dependencies yield estimates of ??c1 that are as much as 75??C beneath those which would be predicted if they were neglected. ?? 1988.

  7. Hydrogen desorption from ball milled MgH2 catalyzed with Fe

    NASA Astrophysics Data System (ADS)

    Bassetti, A.; Bonetti, E.; Pasquini, L.; Montone, A.; Grbovic, J.; Vittori Antisari, M.

    2005-01-01

    In order to obtain faster hydrogen sorption kinetics, MgH2-Fe nanocomposites were prepared by high-energy ball milling. The MgH2 decomposition was studied in samples obtained by changing in a systematic way both the catalyst amount and the degree of microstructural refinement. To this purpose, blends containing increasing Fe concentration have been ball milled in processing conditions able to impart different amount of structural defects. The resulting samples have been characterized by X-ray diffraction to investigate the microstructural features and the phase composition, while the powder morphology and the degree of catalyst dispersion were analyzed by scanning electron microscopy. Differential scanning calorimetry was carried out to characterize the hydrogen desorption behavior of these nanocomposites. Experimental results clearly show that the characteristics of the desorption process are dominated, among other factors, by the morphology of the catalyst dispersion, which in turns depends on the processing conditions and blend composition. In order to achieve low desorption temperatures the homogeneous catalyst dispersion in micron-size particles throughout the structure is required. This condition can be achieved by suitable tuning of the milling conditions and of the catalyst amount.

  8. Deformation induced defects in iron revealed by thermal desorption spectroscopy of tritium

    SciTech Connect

    Nagumo, M.; Ohta, K.; Saitoh, H.

    1999-01-08

    Plastic deformation is deeply involved in fracture phenomena by ways of nucleation of incipient microcrack, ductile crack growth resistance and hydrogen embrittlement. Stress concentration ahead of piled up dislocation arrays, strain incompatibility at grain boundaries or interfaces of second phases and shear linking of microvoids have been generally accepted to take place associated with plastic deformation. Recently, hydrogen thermal desorption spectroscopy (TDS) has been applied for the study of hydrogen trapping in steels. Thermal activation of hydrogen atoms from trapping sites is expected to give information on defects acting as trapping sites from the intensity profile of desorption as a function of temperature and the activation energy of desorption. A benefit of TDS of hydrogen is that point defects the size of which is of atomic scale can be detected from the trapping ability with hydrogen atoms. In the present paper, detection of defects produced during plastic deformation of a ferritic steel has been investigated by means of TDS of tritium which was introduced into deformed samples. Radioactivity of tritium permits to use a small amount of tritium without introducing additional defects on charging into deformed specimens. The significance of TDS as a means of investigating hydrogen embrittlement is also examined.

  9. Adsorption and desorption of nickel(II) ions from aqueous solution by a lignocellulose/montmorillonite nanocomposite.

    PubMed

    Zhang, Xiaotao; Wang, Ximing

    2015-01-01

    A new and inexpensive lignocellulose/montmorillonite (LNC/MMT) nanocomposite was prepared by a chemical intercalation of LNC into MMT and was subsequently investigated as an adsorbent in batch systems for the adsorption-desorption of Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the LNC/MMT nanocomposite were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and time. The results indicated that the maximum adsorption capacity of Ni(II) reached 94.86 mg/g at an initial Ni(II) concentration of 0.0032 mol/L, a solution pH of 6.8, an adsorption temperature of 70C, and adsorption time of 40 min. The represented adsorption kinetics model exhibited good agreement between the experimental data and the pseudo-second-order kinetic model. The Langmuir isotherm equation best fit the experimental data. The structure of the LNC/MMT nanocomposite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), whereas the adsorption mechanism was discussed in combination with the results obtained from scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy analyses (FTIR). The desorption capacity of the LNC/MMT nanocomposite depended on parameters such as HNO3 concentration, desorption temperature, and desorption time. The satisfactory desorption capacity of 81.34 mg/g was obtained at a HNO3 concentration, desorption temperature, and desorption time of 0.2 mol/L, 60 C, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of the LNC/MMT nanocomposite was consistent for five cycles without any appreciable loss in the batch process and confirmed that the LNC/MMT nanocomposite was reusable. The overall study revealed that the LNC/MMT nanocomposite functioned as an effective adsorbent in the detoxification of Ni(II)-contaminated wastewater. PMID:25647398

  10. Adsorption and Desorption of Nickel(II) Ions from Aqueous Solution by a Lignocellulose/Montmorillonite Nanocomposite

    PubMed Central

    Zhang, Xiaotao; Wang, Ximing

    2015-01-01

    A new and inexpensive lignocellulose/montmorillonite (LNC/MMT) nanocomposite was prepared by a chemical intercalation of LNC into MMT and was subsequently investigated as an adsorbent in batch systems for the adsorption-desorption of Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the LNC/MMT nanocomposite were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and time. The results indicated that the maximum adsorption capacity of Ni(II) reached 94.86 mg/g at an initial Ni(II) concentration of 0.0032 mol/L, a solution pH of 6.8, an adsorption temperature of 70°C, and adsorption time of 40 min. The represented adsorption kinetics model exhibited good agreement between the experimental data and the pseudo-second-order kinetic model. The Langmuir isotherm equation best fit the experimental data. The structure of the LNC/MMT nanocomposite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), whereas the adsorption mechanism was discussed in combination with the results obtained from scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy analyses (FTIR). The desorption capacity of the LNC/MMT nanocomposite depended on parameters such as HNO3 concentration, desorption temperature, and desorption time. The satisfactory desorption capacity of 81.34 mg/g was obtained at a HNO3 concentration, desorption temperature, and desorption time of 0.2 mol/L, 60 ºC, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of the LNC/MMT nanocomposite was consistent for five cycles without any appreciable loss in the batch process and confirmed that the LNC/MMT nanocomposite was reusable. The overall study revealed that the LNC/MMT nanocomposite functioned as an effective adsorbent in the detoxification of Ni(II)-contaminated wastewater. PMID:25647398

  11. Desorption of a methamphetamine surrogate from wallboard under remediation conditions

    NASA Astrophysics Data System (ADS)

    Poppendieck, Dustin; Morrison, Glenn; Corsi, Richard

    2015-04-01

    Thousands of homes in the United States are found to be contaminated with methamphetamine each year. Buildings used to produce illicit methamphetamine are typically remediated by removing soft furnishings and stained materials, cleaning and sometimes encapsulating surfaces using paint. Methamphetamine that has penetrated into paint films, wood and other permanent materials can be slowly released back into the building air over time, exposing future occupants and re-contaminating furnishings. The objective of this study was to determine the efficacy of two wallboard remediation techniques for homes contaminated with methamphetamine: 1) enhancing desorption by elevating temperature and relative humidity while ventilating the interior space, and 2) painting over affected wallboard to seal the methamphetamine in place. The emission of a methamphetamine surrogate, N-isopropylbenzylamine (NIBA), from pre-dosed wallboard chambers over 20 days at 32 °C and two values of relative humidity were studied. Emission rates from wallboard after 15 days at 32 °C ranged from 35 to 1400 μg h-1 m-2. Less than 22% of the NIBA was removed from the chambers over three weeks. Results indicate that elevating temperatures during remediation and latex painting of impacted wallboard will not significantly reduce freebase methamphetamine emissions from wallboard. Raising the relative humidity from 27% to 49% increased the emission rates by a factor of 1.4. A steady-state model of a typical home using the emission rates from this study and typical residential building parameters and conditions shows that adult inhalation reference doses for methamphetamine will be reached when approximately 1 g of methamphetamine is present in the wallboard of a house.

  12. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400ngm(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air. PMID:26493981

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

    NASA Astrophysics Data System (ADS)

    Li, Ming; Huang, Xiaobo; Kang, Zhan

    2015-08-01

    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.

  14. Sorption and desorption studies of chromium(VI) from nonviable cyanobacterium Nostoc muscorum biomass.

    PubMed

    Gupta, V K; Rastogi, A

    2008-06-15

    This communication presents results pertaining to the sorptive and desorptive studies carried out on chromium(VI) removal onto nonviable freshwater cyanobacterium (Nostoc muscorum) biomass. Influence of varying the conditions for removal of chromium(VI), such as the pH of aqueous solution, the dosage of biosorbent, the contact time with the biosorbent, the temperature for the removal of chromium, the effect of light metal ions and the adsorption-desorption studies were investigated. Sorption interaction of chromium on to cyanobacterial species obeyed both the first and the second-order rate equation and the experimental data showed good fit with both the Langmuir and freundlich adsorption isotherm models. The maximum adsorption capacity was 22.92 mg/g at 25 degrees C and pH 3.0. The adsorption process was endothermic and the values of thermodynamic parameters of the process were calculated. Various properties of the cyanobacterium, as adsorbent, explored in the characterization part were chemical composition of the adsorbent, surface area calculation by BET method and surface functionality by FTIR. Sorption-desorption of chromium into inorganic solutions and distilled water were observed and this indicated the biosorbent could be regenerated using 0.1 M HNO3 and EDTA with upto 80% recovery. The biosorbents were reused in five biosorption-desorption cycles without a significant loss in biosorption capacity. Thus, this study demonstrated that the cyanobacterial biomass N. muscorum could be used as an efficient biosorbent for the treatment of chromium(VI) bearing wastewater. PMID:18053641

  15. Absorption and desorption of hydrogen, deuterium, and tritium for Zr--V--Fe getter

    SciTech Connect

    Ichimura, K.; Inoue, N.; Watanabe, K.; Takeuchi, T.

    1984-07-01

    Nonevaporable getters have wide applicability for developing the tritium handling techniques for thermonuclear fusion devices. From this viewpoint, mechanisms of the absorption and desorption of hydrogen isotopes and the isotope effects were investigated for a Zr--V--Fe alloy (St-707) by means of the mass analyzed thermal desorption spectroscopy. It was observed that the absorption rate was proportional to the first power of the pressure, indicating that the rate limiting step is the dissociative adsorption of hydrogen isotopes on the surface. The activation energy was very small, in the order of magnitude of a few tens of calories per mole in a temperature range from -196 to 200 /sup 0/C. The desorption rate was proportional to the square of the amount of absorption, indicating that the rate limiting step is the associative desorption reaction of hydrogen atoms or ions diffused to the surface from the bulk. The rate constants for hydrogen and deuterium were determined as k/sub d/(H/sub 2/) = (5.3/sup +2.6//sub -1.7/)exp(-(28.0 +- 0.7) x 10/sup 3//RT) and k/sub d/(D/sub 2/) = (5.0/sup +2.7//sub -1.7/)exp(-(28.6 +- 0.8) x 10/sup 3//RT) in (1/Pa 1 s), respectively, where R is in (cal/mol deg). With regard to tritium, the rate constant was evaluated as k/sub d/(T/sub 2/) = (5.0/sup +20//sub -4.0/)exp(-(29.3 +- 3) x 10/sup 3//RT), however, the frequency factor will have to be corrected by knowing the relative sensitivity factor of the mass spectrometer for tritium (T/sub 2/).

  16. Techniques for improving the accuracy of cyrogenic temperature measurement in ground test programs

    NASA Technical Reports Server (NTRS)

    Dempsey, Paula J.; Fabik, Richard H.

    1993-01-01

    The performance of a sensor is often evaluated by determining to what degree of accuracy a measurement can be made using this sensor. The absolute accuracy of a sensor is an important parameter considered when choosing the type of sensor to use in research experiments. Tests were performed to improve the accuracy of cryogenic temperature measurements by calibration of the temperature sensors when installed in their experimental operating environment. The calibration information was then used to correct for temperature sensor measurement errors by adjusting the data acquisition system software. This paper describes a method to improve the accuracy of cryogenic temperature measurements using corrections in the data acquisition system software such that the uncertainty of an individual temperature sensor is improved from plus or minus 0.90 deg R to plus or minus 0.20 deg R over a specified range.

  17. Retention time prediction of compounds in Grob standard mixture for apolar capillary columns in temperature-programmed gas chromatography.

    PubMed

    Thewalim, Yasar; Aldaeus, Fredrik; Colmsj, Anders

    2009-01-01

    This paper presents an extension of a previous investigation in which the behavior of nonpolar compounds in temperature-programmed gas chromatographic runs was predicted using thermodynamic (entropy and enthalpy) parameters derived from isothermal runs. In a similar manner, entropy and enthalpy parameters were determined for a Grob standard mixture of compounds with widely varying chemical characteristics. These parameters were used to predict the retention times and chromatographic behaviors of the compounds on four gas chromatography capillary columns: three that had phenyl-based stationary phases (with degrees of substitution of 0%, 5% and 50%) and one with (50%) cyanopropyl substitution. The predictions matched data empirically obtained from temperature-programmed chromatographic runs for all of the compounds extremely well, despite the wide variations in polarity of both the compounds and stationary phases. Thus, the results indicate that such simulations could greatly reduce the time and material costs of chromatographic optimizations. PMID:18751687

  18. Non-thermal ion desorption from an acetonitrile (CH3CN) astrophysical ice analogue studied by electron stimulated ion desorption.

    PubMed

    Ribeiro, F de A; Almeida, G C; Garcia-Basabe, Y; Wolff, W; Boechat-Roberty, H M; Rocco, M L M

    2015-11-01

    The incidence of high-energy radiation onto icy surfaces constitutes an important route for leading new neutral or ionized molecular species back to the gas phase in interstellar and circumstellar environments, especially where thermal desorption is negligible. In order to simulate such processes, an acetonitrile ice (CH3CN) frozen at 120 K is bombarded by high energy electrons, and the desorbing positive ions are analyzed by time-of-flight mass spectrometry (TOF-MS). Several fragment and cluster ions were identified, including the Hn=1-3(+), CHn=0-3(+)/NHn=0-1(+); C2Hn=0-3(+)/CHn=0-3N(+), C2Hn=0-6N(+) ion series and the ion clusters (CH3CN)n=1-2(+) and (CH3CN)n=1-2H(+). The energy dependence on the positive ion desorption yield indicates that ion desorption is initiated by Coulomb explosion following Auger electronic decay. The results presented here suggest that non-thermal desorption processes, such as desorption induced by electronic transitions (DIET) may be responsible for delivering neutral and ionic fragments from simple nitrile-bearing ices to the gas-phase, contributing to the production of more complex molecules. The derived desorption yields per electron impact may contribute to chemical evolution models in different cold astrophysical objects, especially where the abundance of CH3CN is expected to be high. PMID:26426125

  19. Effects of H{sub 2}O and H{sub 2}O{sub 2} on thermal desorption of tritium from stainless steel

    SciTech Connect

    Quinlan, M. J.; Shmayda, W. T.; Lim, S.; Salnikov, S.; Chambers, Z.; Pollock, E.; Schroeder, W. U.

    2008-07-15

    Tritiated stainless steel was subjected to thermal desorption at various temperatures, different temperature profiles, and in the presence of different helium carrier gas additives. In all cases the identities of the desorbing tritiated species were characterized as either water-soluble or insoluble. The samples were found to contain 1.1 mCi{+-}0.4 mCi. Approximately ninety-five percent of this activity was released in molecular water-soluble form. Additives of H{sub 2}O or H{sub 2}O{sub 2} to dry helium carrier gas increase the desorption rate and lower the maximum temperature to which the sample must be heated, in order to remove the bulk of the tritium. The measurements validate a method of decontamination of tritiated steel and suggest a technique that can be used to further explore the mechanisms of desorption from tritiated metals. (authors)

  20. Program for the development of high temperature electrical materials and components

    NASA Technical Reports Server (NTRS)

    Neff, W. S.; Lowry, L. R.

    1972-01-01

    Evaluation of high temperature, space-vacuum performance of selected electrical materials and components, high temperature capacitor development, and evaluation, construction, and endurance testing of compression sealed pyrolytic boron nitride slot insulation are described. The first subject above covered the aging evaluation of electrical devices constructed from selected electrical materials. Individual materials performances were also evaluated and reported. The second subject included study of methods of improving electrical performance of pyrolytic boron nitride capacitors. The third portion was conducted to evaluate the thermal and electrical performance of pyrolytic boron nitride as stator slot liner material under varied temperature and compressive loading. Conclusions and recommendations are presented.

  1. Preparation and thermal desorption properties of dc sputtered zirconium-hydrogen-helium thin films

    SciTech Connect

    Wei, Y. C.; Shi, L. Q.; Zhang, L.; He, Z. J.; Zhang, B.; Wang, L. B.

    2008-11-15

    We developed a new approach for preparing hydrogen and helium co-containing zirconium films (Zr-H-He) to simulate aging metal tritides. We also studied the effect of hydrogen on helium behavior, in which we applied direct current magnetron sputtering in a mixture of working gases (helium, argon, and hydrogen). The amount and depth profile of helium and hydrogen trapped in the films were determined using the elastic recoil detection analysis. The microstructure and surface morphology of the Zr-H-He films were studied by x-ray diffraction, transmission electron microscopy, and atomic force microscopy. To investigate the effect of hydrogen on the thermal release behavior of helium in the Zr film, thermal desorption spectrometry (TDS) was used, which revealed a similar desorption behavior to aged tritides. TDS experiments showed that the spectra were constituted by low-temperature peaks around 300 deg. C and high temperature peaks above 750 deg. C. Furthermore, the solid-phase {alpha} to {delta} transformation changed the shapes of the high-temperature peaks related to microstates of helium bubbles and caused the peak with a massive helium release shift toward lower temperature obviously.

  2. Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

    NASA Astrophysics Data System (ADS)

    Leuenberger, M. C.; Schibig, M. F.; Nyfeler, P.

    2015-12-01

    It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1-10 kJ mol-1, compared to chemisorption which ranges from 100 to 1000 kJ mol-1. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO2, CH4, and H2O. The CO2 results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO2 and H2O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO2 amount adsorbed (5.8 × 1019 CO2 molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between -10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2, ranging from 0.0014 to 0.0184 ppm °C-1 for steel cylinders and -0.0002 to -0.0003 ppm °C-1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders points to significantly lower desorption energies than for steel cylinders and due to the small values, they might at least partly be influenced by temperature, permeation from/to sealing materials, and gas-consumption-induced pressure changes. Temperature coefficients for CH4, CO, and H2O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high-precision calibration purposes such as requested in trace gas applications.

  3. EFFECTS OF TEMPERATURE AND PRESSURE ON PARTICLE COLLECTION MECHANISMS: EXPERIMENTAL PROGRAM

    EPA Science Inventory

    The report gives results of a theoretical and experimental investigation of the effects of high temperatures and high pressures (HTPs) on fundamental particle collection mechanisms. It gives experimental results of inertial impaction, cyclone separation, Brownian diffusion, and e...

  4. Experimental and theoretical comparison of gas desorption energies on metallic and semiconducting single-walled carbon nanotubes.

    PubMed

    Mandeltort, Lynn; Chen, De-Li; Saidi, Wissam A; Johnson, J Karl; Cole, Milton W; Yates, John T

    2013-05-22

    Single-walled carbon nanotubes (SWNTs) exhibit high surface areas and precisely defined pores, making them potentially useful materials for gas adsorption and purification. A thorough understanding of the interactions between adsorbates and SWNTs is therefore critical to predicting adsorption isotherms and selectivities. Metallic (M-) and semiconducting (S-) SWNTs have extremely different polarizabilities that might be expected to significantly affect the adsorption energies of molecules. We experimentally and theoretically show that this expectation is contradicted, for both a long chain molecule (n-heptane) and atoms (Ar, Kr, and Xe). Temperature-programmed desorption experiments are combined with van der Waals corrected density functional theory, examining adsorption on interior and exterior sites of the SWNTs. Our calculations show a clear dependence of the adsorption energy on nanotube diameter but not on whether the tubes are conducting or insulating. We find no significant experimental or theoretical difference in adsorption energies for molecules adsorbed on M- and S-SWNTs having the same diameter. Hence, we conclude that the differences in polarizabilities between M- and S-SWNTs have a negligible influence on gas adsorption for spherical molecules as well as for highly anisotropic molecules such as n-heptane. We expect this conclusion to apply to all types of adsorbed molecules where van der Waals interactions govern the molecular interaction with the SWNT. PMID:23627526

  5. Chemisorption, reaction and desorption studies of coal chars in steam, oxygen and carbon dioxide. Final report, January 1986-December 1989

    SciTech Connect

    Radovic, L.R.; Lizzio, A.A.; Jiang, H.

    1990-09-01

    The use of a transient kinetics (TK) technique allowed a direct measurement of reactive surface area (RSA) for chars gasified in both CO{sub 2} and O{sub 2}, i.e., gasification rates normalized with respect to RSA were essentially constant over the entire conversion range. A temperature-programmed desorption (TPD) technique was also used to determine the amount of reactive surface intermediate formed on the chars during gasification in CO{sub 2} and O{sub 2}; the results were in good agreement with those obtained by TK. In addition, TPD allowed an important distinction to be made between the stable C-O complexes and reactive C(O) intermediates residing on the char surface during gasification in CO{sub 2} and O{sub 2}. The application of the two independent but complementary techniques provided a satisfactory quantitative understanding of char reactivity variations with conversion in CO{sub 2} and O{sub 2}. Both techniques possess the unique capability of separately determining the reaction rate constant (site reactivity or turnover frequency) and the number of active sites participating in the reaction (RSA). A comparison of turnover frequencies for different chars gasified in 1 atm CO{sub 2} suggested that char gasification may be a structure sensitive reaction. The concept of reactive surface area was also used to achieve a better quantitative understanding of catalyzed char reactivity variations with conversion in carbon dioxide.

  6. Thermal desorption of CO and H2 from degassed 304 and 347 stainless steel

    NASA Technical Reports Server (NTRS)

    Rezaie-Serej, S.; Outlaw, R. A.

    1994-01-01

    Thermal desorption spectroscopy (TDS), along with Auger electron spectroscopy, was used to study the desorption of H2 and CO from baked 304 and 347 stainless-steel samples exposed only to residual gases. Both 347 and 304 samples gave identical TDS spectra. The spectra for CO contained a sharp leading peak centered in the temperature range 410-440C and an exponentially increasing part for temperatures higher than 500C, with a small peak around 600C appearing as a shoulder. The leading peak followed a second-order desorption behavior with an activation energy of 28+/-2 kcal/mol, suggesting that the rate-limiting step for this peak is most likely a surface reaction that produces the CO molecules in the surface layer. The amount of desorbed CO corresponding to this peak was approximately 0.5X10(exp 14) molecules/cm(exp 2) . The exponentially rising part of the CO spectrum appeared to originate from a bulk diffusion process. The TDS spectrum for H2 consisted of a main peak centered also in the temperature range 410-440C, with two small peaks appearing as shoulders at approximately 500 and 650C. The main peak in this case also displayed a second-order behavior with an activation energy of 14+/-2 kcal/mol. The amount of desorbed H2, approximately 1.9X 10(exp 15) molecules/cm(exp 2) , appeared to be independent of the concentration of hydrogen in the bulk, indicating that the majority of the desorbed H2 originated from the surface layer.

  7. The laser desorption/laser ionization mass spectra of some methylated xanthines and the laser desorption of caffeine and theophylline from thin layer chromatography plates

    NASA Astrophysics Data System (ADS)

    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.

  8. Optimisation of temperature-programmed gas chromatographic separation of organochloride pesticides by response surface methodology.

    PubMed

    D'Archivio, Angelo Antonio; Maggi, Maria Anna; Marinelli, Cristina; Ruggieri, Fabrizio; Stecca, Fabrizio

    2015-12-01

    A response surface methodology (RSM) approach is applied to optimise the temperature-programme gas-chromatographic separation of 16 organochloride pesticides, including 12 compounds identified as highly toxic chemicals by the Stockholm Convention on Persistent Organic Pollutants. A three-parameter relationship describing both linear and curve temperature programmes is derived adapting a model previously used in literature to describe concentration gradients in liquid chromatography with binary eluents. To investigate the influence of the three temperature profile descriptors (the starting temperature, the gradient duration and a shape parameter), a three-level full-factorial design of experiments is used to identify suitable combinations of the above variables spanning over a useful domain. Resolutions of adjacent peaks are the responses modelled by RSM using two alternative methods: a multi-layer artificial network (ANN) and usual polynomial regression. The proposed ANN-based approach permits to model simultaneously the resolutions of all the consecutive analyte pairs as a function of the temperature profile descriptors. Four critical pairs giving partially overlapped peaks are identified and multiresponse optimisation is carried out by analysing the surface plot of a global resolution defined as the average of the resolutions of the critical pairs. Descriptive/predictive performance and applicability of the ANN and polynomial RSM methods are compared and discussed. PMID:26559619

  9. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1992

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  10. Real-time detection of hydrogen absorption and desorption in metallic palladium using vibrating wire method

    NASA Astrophysics Data System (ADS)

    Inagaki, Yuji; Nishimura, Atsuki; Yokooji, Honoka; Takata, Hiroki; Kawae, Tatsuya

    2015-09-01

    A vibrating wire (VW) method was applied to investigate the hydrogen absorption and desorption properties of palladium. At room temperature, a considerable shift in resonance frequency was successfully observed in VW spectra under H2 gas exposure. The shift is reversible in the initial stage of the exposure and is attributed to changes in the density and Young’s modulus of the VW sensor. Irreversibility of the shift because of embrittlement is detected after a sufficient exposure time. H absorption is slowed down enormously at T = 200 K owing to suppression of the thermal activation process.

  11. Application of ASTM E-1559 Apparatus to Study H2O Desorption

    NASA Technical Reports Server (NTRS)

    Woronowicz, Michael; Perry, Radford, III; Meadows, George A.

    2015-01-01

    The NASA James Webb Space Telescope project identified a need to measure water vapor desorption from cryogenic surfaces in order to validate predictions of spacecraft design performance. A review of available scientific literature indicated no such measurements had been reported below 131 K. Contamination control personnel at NASA Goddard Space Flight Center recognized the possibility they readily possessed the means to collect these measurements at lower temperatures using an existing apparatus commonly employed for making outgassing observations. This presentation will relate how the ASTM E-1559 Molekit apparatus was used without physical modification to measure water vapor sublimation down to 120 K and compare this data to existing equilibrium vapor pressure models.

  12. Influence of surface coverage on the chemical desorption process

    SciTech Connect

    Minissale, M.; Dulieu, F.

    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.

  13. Estimating desorption kinetic rates from sequential batch experiments

    SciTech Connect

    Uchrin, C.G.; Greaney, C.M.; Koshy, K.; Wojtenko, I.

    1995-12-31

    A serious limitation in the modeling of the transport and fate of contaminants in soil/water systems is the lack of information regarding the desorption kinetics of substances from contaminated materials. A frequently made assumption is that adsorption/desorption processes are completely reversible and fast, such that a single equilibrium expression can be used to estimate the distribution of a substance between solid and liquid phases. A reliable method for examining desorption kinetics is needed. The paper presents results from an experimental method the authors developed to estimate desorption kinetics of organic substances from contaminated materials. The method involves sequential batch experiments operated in a kinetic mode. A mass of contaminated soil is introduced into a volume of uncontaminated liquid. The systems are studied until they reach an apparent equilibrium, whereupon a new desorption driving force is established by replacing a volume of the now contaminated liquid with an equal volume of uncontaminated liquid. All input and output is accomplished by syringe inclosed vials to minimize losses. The resultant data are modeled using a Marquardt-Levenberg algorithm from which cumulative mass desorbed is modeled as a limited first-order growth process, which fits the data well. Total experimental plus analytical error has been calculated for all experiments to date and is less than 5%. Organic substances studied include benzene, toluene, and meta-xylene and soils include both reference soils and contaminated site soils.

  14. Effect of temperature on lubrication with biobased oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Temperature is an important parameter affecting the performance of lubricant ingredients. It affects such important tribological characteristics as viscosity, film thickness, adsorption, desorption, friction, and wear. Temperature also promotes oxidation, polymerization, and degradation which nega...

  15. Carbon dioxide sorption/ desorption characteristics of coals in Taiwan

    NASA Astrophysics Data System (ADS)

    Chien-Hung, Hsiao; Loung-Yie, Tsai

    2013-04-01

    Geological sequestration of CO2 into depleted oil reservoir, saline aquifer or unmineable coal seam is now being actively investigated for the purpose of reducing greenhouse gas in the atmosphere. Understanding the physical, chemical, and thermodynamic phenomena occurred with CO2 injection is very important in marking a reliable prediction of sequestration. This study examined the feasibility of carbon dioxide sequestration into unmineable coal seams in Taiwan. A total of 20 Miocene-aged coal samples from Western Foothill Belt, NW Taiwan, were collected. The stratigraphy include Mushan, Shihti, and Nanchuang Formation from bottom up. Proximate and petrographic analyses include maceral composition, Vitrinite reflectance were also measured. Carbon dioxide adsorption isotherms were analyzed at 35 degrees Celsius and up to 800 psi, by using a gravimetric ad/desorption apparatus. Isotherms were then fitted with a modified Langmuir Isotherm model by using Langmuir Pressure and Langmuir Volume so the model can be applied to supercritical conditions. According to the result of adsorption experiment, the pressure and temperature were quite significant. The gas storage capacity of CO2 was about 400 600 scf/ton at pressure up to 800 psi. Comparing the results of adsorption capacity with Proximate analysis and vitrinite reflectance, the Langmuir Volume shows a strong positive correlation with fixed carbon and vitrinite content. Furthermore, Adsorption capacity is closely related to micropores which were also rank and maceral dependent. It is noticed that the observed coal pore structures were affected by rank, and then exhibit have different diffusion rate of CO2.Finally, images under SEM were evaluated to understand the pathways of gas sorption.

  16. 13th TOPICAL CONFERENCE ON HIGH TEMPERATURE PLASMA DIAGNOSTICS SCIENTIFIC PROGRAM

    SciTech Connect

    C. BARNES

    2000-07-01

    Electron cyclotron emission (ECE) has been employed as a standard electron temperature profile diagnostic on many tokamaks and stellarators, but most magnetically confined plasma devices cannot take advantage of standard ECE diagnostics to measure temperature. They are either overdense, operating at high density relative to the magnetic field (e.g. {omega}{sub pe} >> {Omega}{sub ce} in a spherical torus) or they have insufficient density and temperature to reach the blackbody condition ({tau} > 2). Electron Bernstein waves (EBWs) are electrostatic waves which can propagate in overdense plasmas and have a high optical thickness at the electron cyclotron resonance layers, as a result of their large K{sub i}. This talk reports on measurements of EBW emission on the CDX-U spherical torus, where B{sub 0} {approx} 2 kG, {approx} 10{sup 13} cm{sup -3} and T{sub e} {approx} 10 - 200 eV. Results will be presented for both direct detection of EBWs and for mode-converted EBW emission. The EBW emission was absolutely calibrated and compared to the electron temperature profile measured by a multi-point Thomson scattering diagnostic. Depending on the plasma conditions, the mode-converted EBW radiation temperature was found to be {le} T{sub e} and the emission source was determined to be radially localized at the electron cyclotron resonance layer. A Langmuir triple probe was employed to measure changes in edge density profile in the vicinity of the upper hybrid resonance where the mode conversion of the EBWs is expected to occur. Changes in the mode conversion efficiency may explain the observation of mode-converted EBW radiation temperatures below T{sub e}. Initial results suggest EBW emission and EBW heating are viable concepts for plasmas where {omega}{sub pe} >> {Omega}{sub ce}.

  17. Sn-Mn binary metal oxides as non-carbon sorbent for mercury removal in a wide-temperature window.

    PubMed

    Xie, Jiangkun; Xu, Haomiao; Qu, Zan; Huang, Wenjun; Chen, Wanmiao; Ma, Yongpeng; Zhao, Songjian; Liu, Ping; Yan, Naiqiang

    2014-08-15

    A series of Sn-Mn binary metal oxides were prepared through co-precipitation method. The sorbents were characterized by powder X-ray diffraction (powder XRD), transmission electronic microscopy (TEM), H2-temperature-programmed reduction (H2-TPR) and NH3-temperature-programmed desorption (NH3-TPD) methods. The capability of the prepared sorbents for mercury adsorption from simulated flue gas was investigated by fixed-bed experiments. Results showed that mercury adsorption on pure SnO2 particles was negligible in the test temperature range, comparatively, mercury capacity on MnOx at low temperature was relative high, but the capacity would decrease significantly when the temperature was elevated. Interestingly, for Sn-Mn binary metal oxide, mercury capacity increased not only at low temperature but also at high temperature. Furthermore, the impact of SO2 on mercury adsorption capability of Sn-Mn binary metal oxides was also investigated and it was noted that the effect at low temperature was different comparing with that of high temperature. The mechanism was investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs). Moreover, a mathematic model was built to calculate mercury desorption activation energy from Sn to Mn binary metal oxides. PMID:24910043

  18. In situ ?+SR measurements on the hydrogen desorption reaction of magnesium hydride

    NASA Astrophysics Data System (ADS)

    Umegaki, I.; Nozaki, H.; Harada, M.; Higuchi, Y.; Noritake, T.; Matsumoto, M.; Towata, S.-i.; Ansaldo, E. J.; Brewer, J. H.; Koda, A.; Miyake, Y.; Sugiyama, J.

    2014-12-01

    In order to clarify the reason why the hydrogen desorption temperature (Td) of MgH2 is lowered by milling, we have studied the change in a local nuclear magnetic field with temperature by means of ?+SR. We have found a very clear oscillation in the ZF-spectrum at 2 K for the "milled" and "milled with Nb2O5" samples, while such oscillation is weaker for the "as prepared" MgH2. It was also found that the oscillation signal is stable up to 250 K and is assigned mainly due to the formation of a H-?-H system. At temperatures above ambient T, we also found that the ZF-?+SR spectrum exhibits a static Kubo-Toyabe behavior due to the nuclear magnetic field of 1H. Furthermore, it was clarified that rapid H diffusion starts well below Td only in the milled samples, leading to the conclusion that the consequent enhanced diffusion rate in MgH2 is essential to accelerate the desorption reaction and to decrease Td.

  19. Results of thermal desorption treatability studies on soils from wood treatment sites

    SciTech Connect

    Shealy, S.E.; Lin, W.C.; Richards, M.K.; Culp, J.

    1997-12-31

    Thermal desorption is one of the most effective technologies for treatment of soils or wastes containing organic contaminants. This includes the polycyclic aromatic hydrocarbons, pentachlorophenol and dioxins/furans that are the typical contaminants of concern at wood treatment sites. This paper summarizes the results of bench-scale thermal desorption treatability studies on soils from two wood treatment sites. The testing identified the time-temperature combination needed for contaminant removal and provided data on the composition of the treatment residuals from the thermal treatment process. This study included testing in static trays and in a small bench-scale rotary kiln. The static tray tests are a bench-scale method of readily evaluating the effect of various target temperatures and residence times on contaminant removal. These tests use 40--50 grams, of soil, which is aliquoted into a tray and placed into a muffle furnace at a pre-determined time and temperature. These tests are used to identify effective treatment conditions. The Rotary Thermal Apparatus (RTA) is also a bench-scale device that is used to treat 1 to 1.5 kilograms of soil in an indirectly heated rotary tube. This device simulates the heat and mass transfer in rotary kiln. The RTA is a batch device and can be purged with nitrogen, oxygen or other gases to simulate the atmosphere of various thermal treatment processes.

  20. Flash Desorption/Mass Spectrometry for the Analysis of Less- and Nonvolatile Samples Using a Linearly Driven Heated Metal Filament

    NASA Astrophysics Data System (ADS)

    Usmanov, Dilshadbek T.; Ninomiya, Satoshi; Hiraoka, Kenzo

    2013-11-01

    In this paper, the important issue of the desorption of less- and nonvolatile compounds with minimal sample decomposition in ambient mass spectrometry is approached using ambient flash desorption mass spectrometry. The preheated stainless steel filament was driven down and up along the vertical axis in 0.3 s. At the lowest position, it touched the surface of the sample with an invasion depth of 0.1 mm in 50 ms (flash heating) and was removed from the surface (fast cooling). The heating rate corresponds to ~104 °C/s at the filament temperature of 500 °C. The desorbed gaseous molecules were ionized by using a dielectric barrier discharge ion source, and the produced ions were detected by a time-of-flight (TOF) mass spectrometer. Less-volatile samples, such as pharmaceutical tablets, narcotics, explosives, and C60 gave molecular and protonated molecule ions as major ions with thermal decomposition minimally suppressed. For synthetic polymers (PMMA, PLA, and PS), the mass spectra reflected their backbone structures because of the suppression of the sequential thermal decompositions of the primary products. The present technique appears to be suitable for high-throughput qualitative analyses of many types of solid samples in the range from a few ng to 10 μg with minimal sample consumption. Some contribution from tribodesorption in addition to thermal desorption was suggested for the desorption processes. [Figure not available: see fulltext.

  1. Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2013-03-01

    This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

  2. EPA AND ERDA HIGH-TEMPERATURE/HIGH-PRESSURE PARTICULATE CONTROL PROGRAMS

    EPA Science Inventory

    The report describes and compares current projects sponsored by EPA and the U.S. Energy Research and Development Administration (ERDA), relating to the control of particulate matter in fuel gas streams at high temperatures (1000 to 2000F) and high pressures (5 atm and greater). T...

  3. Controlling particulates, temperature, and tritium in an inert glovebox for a weapons program

    SciTech Connect

    Purson, J.D.; Powers, D.; Walthers, C.; Navarro, C.; Newman, E.; Romero, J.; Jenkins, R.

    1996-07-01

    A glovebox is described in which several environmental parameters are controlled and monitored. Included in these are particulate, tritium, water vapor, oxygen and temperature. The paper details the design rationale and process and describes the glovebox, presently in use for neutron generator production.

  4. Temperature Control with Two Parallel Small Loop Heat Pipes for GLM Program

    NASA Technical Reports Server (NTRS)

    Khrustalev, Dmitry; Stouffer, Chuck; Ku, Jentung; Hamilton, Jon; Anderson, Mark

    2014-01-01

    The concept of temperature control of an electronic component using a single Loop Heat Pipe (LHP) is well established for Aerospace applications. Using two LHPs is often desirable for redundancy/reliability reasons or for increasing the overall heat source-sink thermal conductance. This effort elaborates on temperature controlling operation of a thermal system that includes two small ammonia LHPs thermally coupled together at the evaporator end as well as at the condenser end and operating "in parallel". A transient model of the LHP system was developed on the Thermal Desktop (TradeMark) platform to understand some fundamental details of such parallel operation of the two LHPs. Extensive thermal-vacuum testing was conducted with two thermally coupled LHPs operating simultaneously as well as with only one LHP operating at a time. This paper outlines the temperature control procedures for two LHPs operating simultaneously with widely varying sink temperatures. The test data obtained during the thermal-vacuum testing, with both LHPs running simultaneously in comparison with only one LHP operating at a time, are presented with detailed explanations.

  5. Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

    NASA Astrophysics Data System (ADS)

    berg, H.; Gladh, J.; Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Fhlisch, A.; Katayama, T.; Kaya, S.; LaRue, J.; Mgelhj, A.; Nordlund, D.; Ogasawara, H.; Schlotter, W. F.; Sellberg, J. A.; Sorgenfrei, F.; Turner, J. J.; Wolf, M.; Wurth, W.; strm, H.; Nilsson, A.; Nrskov, J. K.; Pettersson, L. G. M.

    2015-10-01

    We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (< 100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of ~ 2000 K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (~ 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate.

  6. Energy audit of three energy-conserving devices in a steel industry demonstration program. Task III. GTE high temperature recuperation

    SciTech Connect

    Holden, F.C.; Hoffman, A.O.; Lownie, H.W.

    1983-06-01

    The Office of Industrial Programs of the Department of Energy has undertaken a program to demonstrate to industry the benefits of installing various energy-conserving devices and equipment. This report presents results on one of those systems, a high-temperature ceramic recuperator designed and manufactured by Sylvania Chemical and Metallurgical Division, GTE Products Corporation of Towanda, Pennsylvania. The ceramic cross-flow recuperator unit recovers waste heat from the hot combustion gases and delivers preheated air to high-temperature burners of various manufacture. Of the 38 host site installations included in the program, sufficient operating data were obtained from 28 sites to evaluate the benefits in terms of energy and economic savings that can be achieved. Performance and cost data are analyzed and presented for those 28 installations, which covered a variety of applications, sizes, and industry types. Except for 5 sites where unusual operating or data-collection problems were encountered, the improvements in performance of the recuperated furnaces equalled or exceeded estimates; the average of the total fuel savings for these 23 sites was 44.0 percent, some portion of which resulted from furnace improvements other than recuperation. Payback times were calculated for both total costs and for recuperator-related costs, using a cumulative annual after-tax cash flow method which includes tax investment credits, estimates of general and fuel-price inflation, and maintenance costs.

  7. Desorption mass spectrometry for nonvolatile compounds using an ultrasonic cutter.

    PubMed

    Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T; Hiraoka, Kenzo

    2014-07-01

    In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique. PMID:24833356

  8. Laser-induced acoustic desorption of natural and functionalized biochromophores.

    PubMed

    Sezer, Uğur; Wörner, Lisa; Horak, Johannes; Felix, Lukas; Tüxen, Jens; Götz, Christoph; Vaziri, Alipasha; Mayor, Marcel; Arndt, Markus

    2015-06-01

    Laser-induced acoustic desorption (LIAD) has recently been established as a tool for analytical chemistry. It is capable of launching intact, neutral, or low charged molecules into a high vacuum environment. This makes it ideally suited to mass spectrometry. LIAD can be used with fragile biomolecules and very massive compounds alike. Here, we apply LIAD time-of-flight mass spectrometry (TOF-MS) to the natural biochromophores chlorophyll, hemin, bilirubin, and biliverdin and to high mass fluoroalkyl-functionalized porphyrins. We characterize the variation in the molecular fragmentation patterns as a function of the desorption and the VUV postionization laser intensity. We find that LIAD can produce molecular beams an order of magnitude slower than matrix-assisted laser desorption (MALD), although this depends on the substrate material. Using titanium foils we observe a most probable velocity of 20 m/s for functionalized molecules with a mass m = 10,000 Da. PMID:25946522

  9. Laser-Induced Acoustic Desorption of Natural and Functionalized Biochromophores

    PubMed Central

    2015-01-01

    Laser-induced acoustic desorption (LIAD) has recently been established as a tool for analytical chemistry. It is capable of launching intact, neutral, or low charged molecules into a high vacuum environment. This makes it ideally suited to mass spectrometry. LIAD can be used with fragile biomolecules and very massive compounds alike. Here, we apply LIAD time-of-flight mass spectrometry (TOF-MS) to the natural biochromophores chlorophyll, hemin, bilirubin, and biliverdin and to high mass fluoroalkyl-functionalized porphyrins. We characterize the variation in the molecular fragmentation patterns as a function of the desorption and the VUV postionization laser intensity. We find that LIAD can produce molecular beams an order of magnitude slower than matrix-assisted laser desorption (MALD), although this depends on the substrate material. Using titanium foils we observe a most probable velocity of 20 m/s for functionalized molecules with a mass m = 10?000 Da. PMID:25946522

  10. Laser Control of Product Electronic State: Desorption from Alkali Halides

    SciTech Connect

    Beck, Kenneth M.); Joly, Alan G.); Dupuis, Nicholas F.; Perozzo, Peggy; Hess, Wayne P.); Sushko, P V.; Shluger, Alexander L.

    2004-02-01

    We demonstrate laser control of the electronic product state distribution of photodesorbed halogen atoms from alkali halide crystals. Our general model of surface exciton desorption dynamics is developed into a simple method for laser control of the relative halogen atom spin orbit laser desorption yield. By tuning the excitation laser photon energy in a narrow region of the absorption threshold, the relative Cl(2P1/2) yield can be made to vary from near 0 to 80% from KCI and from near 0 to 60% for NaCl. We described the physical properties necessary to obtain a high degree of product state control and the limitation induced when these requirements are not met. These results demonstrate that laser control can be applied to solid state surface reactions and provide strong support for surface exciton-based desorption models.

  11. Desorption of chemisorbed Carbon on Mo(1 0 0) by noble gas ion sputtering: Validation of ground test measurements of ion engine lifetimes

    NASA Astrophysics Data System (ADS)

    Ho, Chih-Sung; Banerjee, Santanu; Koel, Bruce E.; Duchemin, Olivier B.; Polk, James E.

    2006-02-01

    We report desorption cross section measurements for one monolayer of chemisorbed carbon on a Mo(1 0 0) surface induced by sputtering with noble gas ions (Ne +, Ar +, Xe +) at different incident angles, ion energies, and substrate temperatures. Desorption cross sections were determined by using low-energy ion scattering (LEIS) to monitor the increase of the signal from the Mo substrate. A monolayer of p(1 1) carbon adatoms on the Mo(1 0 0) surface was created by dosing ethylene (C 2H 4) to the substrate at 800 K, and characterized by Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). We find that the carbon desorption cross section increases with increasing mass and energy of the impinging ions, and there is a maximum value for the desorption cross section at an incident angle for the ions of 30 from the surface plane. The desorption cross section also increases up to a substrate temperature of 300 C. Values for the carbon desorption cross section for carbon adatoms on Mo(1 0 0) by 400-eV Xe + ion sputtering are about 2 10 -15 cm 2, which is one order of magnitude higher than those for bulk carbon samples. This information is particularly important for evaluation of ion-engine lifetimes from ground-test measurements in which contaminant carbon is deposited on Mo accelerator grids, potentially altering the sputtering rate of the Mo. Our measurements show that monolayer amounts of carbon on Mo have desorption cross sections that are two orders of magnitude higher than estimates of what would be required to reduce the Mo erosion rate, and thus ground-test measurements can be used with confidence to predict ion-engine wear in space, from this perspective.

  12. NOVEL CERAMIC MEMBRANE FOR HIGH TEMPERATURE CARBON DIOXIDE SEPARATION

    SciTech Connect

    Jun-ichi Ida; Zhaohui Yang; Jerry Y.S. Lin

    2001-09-01

    The Objective of this research program is to develop a dense, non porous ceramic membrane for separation of carbon dioxide from flue gas at high temperatures (400-600 C). The research has been focused on addressing several fundamental issues of lithium zirconate (Li{sub 2}ZrO{sub 3}). In the 2nd half research, we conducted various kinds of experiments to understand the CO{sub 2} sorption/desorption mechanism on the pure and modified Li{sub 2}ZrO{sub 3} with the help of TGA, DSC TGA and XRD. DSC TGA results suggest that the melting of Li/K carbonates mixture may play an important role in rapid CO{sub 2} sorption in the case of modified lithium zirconate. The CO{sub 2} desorption experiments show that CO{sub 2} desorption from the modified lithium zirconate follows the same mechanism as that from the pure lithium zirconate. This is different from the CO{sub 2} adsorption on the pure and modified lithium zirconates.

  13. Characterization of hydrogen absorption/desorption states on lithium-carbon-hydrogen system by neutron diffraction

    NASA Astrophysics Data System (ADS)

    Miyaoka, Hiroki; Itoh, Keiji; Fukunaga, Toshiharu; Ichikawa, Takayuki; Kojima, Yoshitsugu; Fuji, Hironobu

    2008-09-01

    The nanostructural hydrogenated graphite (CnanoHx) was synthesized from graphite by ball milling under hydrogen (H2) atmosphere. In this product, characteristic hydrogenated states in the form of polarized hydrocarbon groups (?CH, ?CH2, and ?CH3) are realized in the nanoscale. By synthesizing the composite of CnanoHx and lithium hydride (LiH), known as the Li ?C?H system, hydrogen was desorbed at 350C, which is a lower temperature compared to the decomposition temperature of each component. It is considered that this hydrogen desorption would be induced by destabilization of each hydrogen absorbed state due to an interaction between the polarized C ?H groups in CnanoHx and LiH. Therefore, in order to understand the hydrogen absorption/desorption mechanism of the Li ?C?H system, it is an important issue to investigate the change in the C ?H groups during hydrogen absorption/desorption reactions in the composite. The correlations among atoms contained in this composite are examined by neutron diffraction measurements, where the protium/deuterium (H/D) isotopic substitution was used to clarify the location of hydrogen atoms in this composite. Some C ?D and Li ?D correlations are found from the radial distribution function [RDF(r)] obtained by the neutron diffraction for the CnanoDx and LiD composite. After dehydrogenation, C ?C triple bond and Li ?C bond, ascribed to lithium carbide (Li2C2), are observed. Furthermore, the RDF(r ) corresponding to rehydrogenated composite indicates the presence of not only the Li ?D correlation but also the C ?D one.

  14. Summary Report on FY12 Small-Scale Test Activities High Temperature Electrolysis Program

    SciTech Connect

    James O'Brien

    2012-09-01

    This report provides a description of the apparatus and the single cell testing results performed at Idaho National Laboratory during January–August 2012. It is an addendum to the Small-Scale Test Report issued in January 2012. The primary program objectives during this time period were associated with design, assembly, and operation of two large experiments: a pressurized test, and a 4 kW test. Consequently, the activities described in this report represent a much smaller effort.

  15. Explosive desorption of icy grain mantles in dense clouds

    NASA Technical Reports Server (NTRS)

    Schutte, W. A.; Greenberg, J. M.

    1991-01-01

    The cycling of the condensible material in dense clouds between the gas phase and the icy grain mantles is investigated. In the model studied, desorption of the ice occurs due to grain mantle explosions when photochemically stored energy is released after transient heating by a cosmic ray particle. It is shown that, depending on the grain size distribution in dense clouds, explosive desorption can maintain up to about eight percent of the carbon in the form of CO in the gas phase at typical cloud densities.

  16. A Computer Program for the Computation of Running Gear Temperatures Using Green's Function

    NASA Technical Reports Server (NTRS)

    Koshigoe, S.; Murdock, J. W.; Akin, L. S.; Townsend, D. P.

    1996-01-01

    A new technique has been developed to study two dimensional heat transfer problems in gears. This technique consists of transforming the heat equation into a line integral equation with the use of Green's theorem. The equation is then expressed in terms of eigenfunctions that satisfy the Helmholtz equation, and their corresponding eigenvalues for an arbitrarily shaped region of interest. The eigenfunction are obtalned by solving an intergral equation. Once the eigenfunctions are found, the temperature is expanded in terms of the eigenfunctions with unknown time dependent coefficients that can be solved by using Runge Kutta methods. The time integration is extremely efficient. Therefore, any changes in the time dependent coefficients or source terms in the boundary conditions do not impose a great computational burden on the user. The method is demonstrated by applying it to a sample gear tooth. Temperature histories at representative surface locatons are given.

  17. State-coupled low temperature geothermal resource assessment program, fiscal year 1982. Final Technical Report

    SciTech Connect

    Icerman, Larry

    1983-08-01

    This report summarizes the results of low-temperature geothermal energy resource assessment efforts in New Mexico during the period from June 15, 1981 through September 30, 1983, under the sponsorship of the US Department of Energy (Contract DE-AS07-78ID01717). The report is divided into four chapters which correspond to the tasks delineated in the contract. Chapter 5 is a brief summary of the tasks performed under this contract during the period October 1, 1978, through June 30, 1983. This work extends the knowledge of low-temperature geothermal reservoirs with the potential for direct heating applications in New Mexico. The research effort focused on compiling basic geothermal data throughout selected areas in New Mexico in a format suitable for direct transfer to the US Geological Survey for inclusion in the GEOTHERM data file and to the National Oceanic and Atmospheric Administration for use with New Mexico geothermal resources maps.

  18. An easy-to-use simulation program demonstrates variations in bacterial cell cycle parameters depending on medium and temperature.

    PubMed

    Stokke, Caroline; Flåtten, Ingvild; Skarstad, Kirsten

    2012-01-01

    Many studies are performed on chromosome replication and segregation in Escherichia coli and other bacteria capable of complex replication with C phases spanning several generations. For such investigations an understanding of the replication patterns, including copy numbers of origins and replication forks, is crucial for correct interpretation of the results.Flow cytometry is an important tool for generation of experimental DNA distributions of cell populations. Here, a Visual Basic based simulation program was written for the computation of theoretical DNA distributions for different choices of cell cycle parameters (C and D phase durations, doubling time etc). These cell cycle parameters can be iterated until the best fit between the experimental and theoretical DNA histograms is obtained. The Excel file containing the simulation software is attached as supporting information.Cultures of Escherichia coli were grown at twelve different media and temperature conditions, with following measurements by flow cytometry and simulation of the DNA distributions. A good fit was found for each growth condition by use of our simulation program. The resulting cell cycle parameters displayed clear inter-media differences in replication patterns, but indicated a high degree of temperature independence for each medium. The exception was the poorest medium (acetate), where the cells grew with overlapping replication cycles at 42 °C, but without at the lower temperatures.We have developed an easy-to-use tool for determination of bacteria's cell cycle parameters, and consequently the cells' chromosome configurations. The procedure only requires DNA distribution measurements by flow cytometry. Use of this simulation program for E. coli cultures shows that even cells growing quite slowly can have overlapping replication cycles. It is therefore always important not only to assume cells' replication patterns, but to actually determine the cell cycle parameters when changing growth conditions. PMID:22348034

  19. Results of an interlaboratory fatigue test program conducted on alloy 800H at room and elevated temperatures

    NASA Technical Reports Server (NTRS)

    Ellis, J. R.

    1985-01-01

    The experimental approach adopted for low cycle fatigue tests of alloy 800H involved the use of electrohydraulic test systems, hour glass geometry specimens, diametral extensometers, and axial strain computers. Attempts to identify possible problem areas were complicated by the lack of reliable data for the heat of Alloy 800H under investigation. The method adopted was to generate definitive test data in an Interlaboratory Fatigue Test Program. The laboratories participating in the program were Argonne National Laboratory, Battelle Columbus, Mar-Test, and NASA Lewis. Fatigue tests were conducted on both solid and turbular specimens at temperatures of 20, 593, and 760 C and strain ranges of 2.0, 1.0, and 0.5 percent. The subject test method can, under certain circumstances, produce fatigue data which are serious in error. This approach subsequently was abandoned at General Atomic Company in favor of parallel gage length specimens and axial extensiometers.

  20. Results of an interlaboratory fatigue test program conducted on alloy 800H at room and elevated temperatures

    NASA Technical Reports Server (NTRS)

    Ellis, J. R.

    1987-01-01

    The experimental approach adopted for low cycle fatigue tests of alloy 800H involved the use of electrohydraulic test systems, hour glass geometry specimens, diametral extensometers, and axial strain computers. Attempts to identify possible problem areas were complicated by the lack of reliable data for the heat of Alloy 800H under investigation. The method adopted was to generate definitive test data in an Interlaboratory Fatigue Test Program. The laboratories participating in the program were Argonne National Laboratory, Battelle Columbus, Mar-Test, and NASA Lewis. Fatigue tests were conducted on both solid and turbular specimens at temperatures of 20, 593, and 760 C and strain ranges of 2.0, 1.0, and 0.5 percent. The subject test method can, under certain circumstances, produce fatigue data which are serious in error. This approach subsequently was abandoned at General Atomic Company in favor of parallel gage length specimens and axial extensometers.

  1. Tunneling Desorption of Single Hydrogen on the Surface of Titanium Dioxide.

    PubMed

    Minato, Taketoshi; Kajita, Seiji; Pang, Chi-Lun; Asao, Naoki; Yamamoto, Yoshinori; Nakayama, Takashi; Kawai, Maki; Kim, Yousoo

    2015-07-28

    We investigated the reaction mechanism of the desorption of single hydrogen from a titanium dioxide surface excited by the tip of a scanning tunneling microscope (STM). Analysis of the desorption yield, in combination with theoretical calculations, indicates the crucial role played by the applied electric field. Instead of facilitating desorption by reducing the barrier height, the applied electric field causes a reduction in the barrier width, which, when coupled with the electron excitation induced by the STM tip, leads to the tunneling desorption of the hydrogen. A significant reduction in the desorption yield was observed when deuterium was used instead of hydrogen, providing further support for the tunneling-desorption mechanism. PMID:26158720

  2. A report on the use of thermal scanner data in an operational program for monitoring apparent rooftop temperatures

    NASA Technical Reports Server (NTRS)

    Bjorklund, J.; Schmer, F. A.; Isakson, R. E.

    1975-01-01

    CENGAS, a division of Central Telephone and Utilities Corporation in cooperation with the Remote Sensing Institute, South Dakota State University, is using airborne thermal scanner data to monitor relative rooftop temperatures. Four Nebraska communities and one South Dakota community were surveyed by the Remote Sensing Institute for CENGAS. Thermal scanner data were converted to a film format and the resultant imagery has been successfully employed by CENGAS. The program places emphasis on heat losses resulting from inadequate home insulation, offers CENGAS customers the opportunity to observe a thermogram of their rooftop, and assists homeowners in evaluating insulation needs.

  3. Real-time studies of gallium adsorption and desorption kinetics on sapphire (0001) by grazing incidence small-angle x-ray scattering and x-ray fluorescence

    SciTech Connect

    Wang Yiyi; Oezcan, Ahmet S.; Ludwig, Karl F.; Bhattacharyya, Anirban

    2008-05-15

    Gallium adsorption and desorption on c-plane sapphire has been studied by real-time grazing incidence small-angle x-ray scattering and x-ray fluorescence as a function of substrate temperature (680-740 deg. C) and Ga flux. The x-ray techniques monitor the surface morphology evolution and amount of Ga on the surface. During deposition, nanodroplets of liquid Ga are observed to form on the surface and coarsen. The growth of droplet size during continuous deposition follows dynamical scaling, in agreement with expectations from theory and simulations which include deposition-induced droplet coalescence. However, observation of continued droplet distance scale coarsening during desorption points to the necessity of including further physical processes in the modeling. The desorption rate at different substrate temperatures gives the activation energy of Ga desorption as 2.7 eV, comparable to measured activation energies for desorption from Ga droplets on other substrates and to the Ga heat of vaporization.

  4. Real-Time Studies of Gallium Adsorption and Desorption Kinetics by Grazing-Incidence Small-Angle X-ray Scattering and X-ray Fluorescence

    SciTech Connect

    Wang, Y.; Ozcan, A; Ludwig, K; Bhattacharyya, A

    2008-01-01

    Gallium adsorption and desorption on c-plane sapphire has been studied by real-time grazing incidence small-angle x-ray scattering and x-ray fluorescence as a function of substrate temperature (680-740 C) and Ga flux. The x-ray techniques monitor the surface morphology evolution and amount of Ga on the surface. During deposition, nanodroplets of liquid Ga are observed to form on the surface and coarsen. The growth of droplet size during continuous deposition follows dynamical scaling, in agreement with expectations from theory and simulations which include deposition-induced droplet coalescence. However, observation of continued droplet distance scale coarsening during desorption points to the necessity of including further physical processes in the modeling. The desorption rate at different substrate temperatures gives the activation energy of Ga desorption as 2.7 eV, comparable to measured activation energies for desorption from Ga droplets on other substrates and to the Ga heat of vaporization.

  5. Programs.

    ERIC Educational Resources Information Center

    Community College Journal, 1996

    1996-01-01

    Includes a collection of eight short articles describing model community college programs. Discusses a literacy program, a mobile computer classroom, a support program for at-risk students, a timber-harvesting program, a multimedia presentation on successful women graduates, a career center, a collaboration with NASA, and an Israeli engineering

  6. Programs.

    ERIC Educational Resources Information Center

    Community College Journal, 1996

    1996-01-01

    Includes a collection of eight short articles describing model community college programs. Discusses a literacy program, a mobile computer classroom, a support program for at-risk students, a timber-harvesting program, a multimedia presentation on successful women graduates, a career center, a collaboration with NASA, and an Israeli engineering…

  7. Optimized thermal desorption for improved sensitivity in trace explosives detection by ion mobility spectrometry.

    PubMed

    Najarro, Marcela; Dávila Morris, Melissa E; Staymates, Matthew E; Fletcher, Robert; Gillen, Greg

    2012-06-01

    In this work we evaluate the influence of thermal desorber temperature on the analytical response of a swipe-based thermal desorption ion mobility spectrometer (IMS) for detection of trace explosives. IMS response for several common high explosives ranging from 0.1 ng to 100 ng was measured over a thermal desorber temperature range from 60 °C to 280 °C. Most of the explosives examined demonstrated a well-defined maximum IMS signal response at a temperature slightly below the melting point. Optimal temperatures, giving the highest IMS peak intensity, were 80 °C for trinitrotoluene (TNT), 100 °C for pentaerythritol tetranitrate (PETN), 160 °C for cyclotrimethylenetrinitramine (RDX) and 200 °C for cyclotetramethylenetetranitramine (HMX). By modifying the desorber temperature, we were able to increase cumulative IMS signal by a factor of 5 for TNT and HMX, and by a factor of 10 for RDX and PETN. Similar signal enhancements were observed for the same compounds formulated as plastic-bonded explosives (Composition 4 (C-4), Detasheet, and Semtex). In addition, mixtures of the explosives exhibited similar enhancements in analyte peak intensities. The increases in sensitivity were obtained at the expense of increased analysis times of up to 20 seconds. A slow sample heating rate as well as slower vapor-phase analyte introduction rate caused by low-temperature desorption enhanced the analytical sensitivity of individual explosives, plastic-bonded explosives, and explosives mixtures by IMS. Several possible mechanisms that can affect IMS signal response were investigated such as thermal degradation of the analytes, ionization efficiency, competitive ionization from background, and aerosol emission. PMID:22498665

  8. Adsorption and desorption of noble gases on activated charcoal: II. sup 222 Rn studies in a monolayer and packed bed

    SciTech Connect

    Scarpitta, S.C.; Harley, N.H. )

    1990-10-01

    The adsorptive and desorptive characteristics of canisters containing a petroleum-based charcoal were investigated under controlled conditions of temperature, relative humidity, and Rn concentration. Charcoals exposed in a monolayer and packed bed during exposure intervals of 1-7 d demonstrate that Rn adsorption and desorption are dependent on bed depth and the amount of water adsorbed. Changes in the adsorptive and desorptive properties of the charcoal occurred near the break-point where the pores became occluded by water vapor that condenses in the entrance capillaries. Radon-222 adsorption is decreased by an order of magnitude as the amount of adsorbed water exceeds the break-point of the charcoal. The reduction in pore surface due to adsorbed water results in a marked increase in the rate of Rn loss from exposed canisters, accounting for reduced adsorption. The apparent desorption time-constant for a 2-cm bed of loose Witco 6 x 10 mesh charcoal containing 0.220-0.365 kg H{sub 2}O kg-1 is typically between 2-8 h. The apparent desorption time-constant for an equivalent packed bed containing a water vapor content of 0.026-0.060 kg H{sub 2}O kg-1, which is below the break-point of the charcoal, is about 15-30 h. Conventional charcoal canisters, if exposed in the fully-opened configuration, can achieve the break-point in less than 4 d at 70% humidity. The use of a diffusion barrier would allow for longer exposure times until the break-point of the charcoal is achieved.

  9. Adsorption and desorption of thermally generated hydrogen atoms on Au(111) and Ag/Au(111)

    NASA Astrophysics Data System (ADS)

    Luh, Dah-An; Li, Kun-Rong; Huang, Ren-Yu; Chen, Ching-Hung; Cheng, Cheng-Maw; Tsuei, Ku-Ding; Wang, Chia-Hsin; Yang, Yaw-Wen

    2015-05-01

    To explore the possibility of employing thermally generated H atoms to determine the chemical composition of a metallic surface, we investigated the adsorption and desorption of H atoms generated with a thermal cracker on surfaces Au(111) and Ag/Au(111). Angle-resolved photoemission spectra showed that the noble-metallic surfaces deteriorated upon exposure to a flux of H atoms at ~ 100 K. Upon subsequent annealing, the order of the surfaces was mostly recovered when H atoms on the surfaces desorbed, but the recovery was incomplete even with annealing at a temperature much higher than that at which H atoms desorb. X-ray photoemission spectra showed that O-containing contaminants existed on the surfaces after the H dosing. The evolution of O 1s during annealing indicated that the O-containing contaminants were H2O and its moieties generated during thermal cracking; the disturbances of the surfaces remaining above the desorption temperature of H atoms were likely caused by chemisorbed O. Our results show that it is possible to employ thermally generated H atoms to determine the chemical composition of a metallic surface, but a small proportion of H2O in a H2 gas line might be unavoidable; precautions against possible O contamination are required when a thermal cracker is employed.

  10. Sorption-desorption of carbamazepine by palygorskite-montmorillonite (PM) filter medium.

    PubMed

    Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D; Stalcup, Apryll

    2015-01-23

    Palygorskite-montmorillonite (PM) was studied as a potential sewage treatment effluent filter material for carbamazepine. Batch sorption experiments were conducted as a function of granule size (0.3-0.6, 1.7-2.0 and 2.8mm) and different sewage effluent conditions (pH, ionic strength and temperature). Results showed PM had a mix of fibrous and plate-like morphologies. Sorption and desorption isotherms were fitted to the Freundlich model. Sorption is granule size-dependent and the medium granule size would be an appropriate size for optimizing both flow and carbamazepine retention. Highest and lowest sorption capacities corresponded to the smallest and the largest granule sizes, respectively. The lowest and the highest equilibrium aqueous (Ce) and sorbed (qe) carbamazepine concentrations were 0.4 mg L(-1) and 4.5 mg L(-1), and 0.6 mg kg(-1) and 411.8 mg kg(-1), respectively. Observed higher relative sorption at elevated concentrations with a Freundlich exponent greater than one, indicated cooperative sorption. The sorption-desorption hysteresis (isotherm non-singularity) indicated irreversible sorption. Higher sorption observed at higher rather than at lower ionic strength conditions is likely due to a salting-out effect. Negative free energy and the inverse sorption capacity-temperature relationship indicated the carbamazepine sorption process was favorable or spontaneous. Solution pH had little effect on sorption. PMID:25439731

  11. Vapor phase adsorption-desorption of 1,1,1-trichloroethane on dry soil

    SciTech Connect

    Dural, N.H.; Chen, C.H.

    1995-12-31

    Vapor phase adsorption of 1,1,1-trichloroethane (TCA) on dry soils was studied at 288, 293, and 298 K. Using a gravimetric adsorption apparatus adsorption/desorption isotherms of TCA were generated on two representing soil samples with different physical/chemical characteristics. Influence of temperature and soil properties were investigated. Isosteric heats of adsorption were calculated and heat curves were established. The experimental data were correlated by the Polanyi Potential, the BET, and the GAB models. Equilibrium isotherms of TCA on both soils were Type 2, characterizing vapor condensation to form multilayers, and they exhibited hysteresis upon desorption. A positive correlation between the soil`s specific surface area and its sorption capacity was observed. Clay content and pore size were also dominating factors. Thermal data showed that the adsorption of TCA vapor on soil was primarily due to physical forces and both samples exhibited energetically heterogeneous surfaces. Results followed the Potential Theory satisfactorily and led to a single temperature-independent characteristic curve for each soil-TCA pair. The BET equation gave accurate correlations for up to 40 % of the saturation pressure, while the GAB equation provided superior correlation of the data for the entire relative pressure range.

  12. Dispersive micro solid-phase extraction for the rapid analysis of synthetic polycyclic musks using thermal desorption gas chromatography-mass spectrometry.

    PubMed

    Chung, Wu-Hsun; Tzing, Shin-Hwa; Ding, Wang-Hsien

    2013-09-13

    A simple and solvent-free method for the rapid analysis of five synthetic polycyclic musks in water samples is described. The method involves the use of dispersive micro solid-phase extraction (D-?-SPE) coupled with direct thermal desorption (TD) gas chromatography-mass spectrometry (GC-MS) operating in the selected-ion-storage (SIS) mode. The parameters affecting the extraction efficiency of the target analytes from water sample and the thermal desorption conditions in the GC injection-port were optimized using a central composite design method. The optimal extraction conditions involved immersing 3.2mg of a typical octadecyl (C18) bonded silica adsorbent (i.e., ENVI-18) in a 10mL water sample. After extraction by vigorously shaking for 1.0min, the adsorbents were collected and dried on a filter. The adsorbents were transferred to a micro-vial, which was directly inserted into GC temperature-programmed injector, and the extracted target analytes were then thermally desorbed in the GC injection-port at 337C for 3.8min. The limits of quantitation (LOQs) were determined to be 1.2-3.0ng/L. Precision, as indicated by relative standard deviations (RSDs), was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 and 90%. A preliminary analysis of the river water samples revealed that galaxolide (HHCB) and tonalide (AHTN) were the two most common synthetic polycyclic musks present. Using a standard addition method, their concentrations were determined to in the range from 11 to 140ng/L. PMID:23932027

  13. Fast screening of pesticide multiresidues in aqueous samples by dual stir bar sorptive extraction-thermal desorption-low thermal mass gas chromatography-mass spectrometry.

    PubMed

    Ochiai, Nobuo; Sasamoto, Kikuo; Kanda, Hirooki; Nakamura, Sadao

    2006-10-13

    A method for fast screening of pesticide multiresidues in aqueous samples using dual stir bar sorptive extraction-thermal desorption-low thermal mass gas chromatography-mass spectrometry (dual SBSE-TD-LTM-GC-MS) has been developed. Recovery of 82 pesticides - organochlorine, carbamate, organophosphorous, pyrethroid and others - for the SBSE was evaluated as a function of octanol-water distribution coefficients (log K(o/w): 1.7-8.35), sample volume (2-20 mL), salt addition (0-30% NaCl), and methanol addition (0-20%). The optimized method consists of a dual SBSE performed simultaneously on respectively a 20-mL sample containing 30% NaCl and a 20-mL sample without modifier (100% sample solution). One extraction with 30% NaCl is mainly targeting solutes with low K(o/w) (log K(o/w)<3.5) and another extraction with unmodified sample solution is targeting solutes with medium and high K(o/w) (log K(o/w)>3.5). After extraction, the two stir bars are placed in a single glass desorption liner and are simultaneously desorbed. The desorbed compounds are analyzed by use of LTM-GC-MS with fast temperature programming (75 degrees C min(-1)) using a 0.18 mm i.d. narrow-bore capillary column and fast scanning (10.83 scan s(-1)) using quadrupole MS. The method showed good linearity (r(2)>0.9900) and high sensitivity (limit of detection: <10 ng L(-1)) for most of the target pesticides. The method was applied to the determination of pesticides at nanograms per liter levels in river water and brewed green tea. PMID:16814312

  14. Development of Designer Diamond Anvils for High Pressure-High-Temperature Experiments in Support of the Stockpile Stewardship Program

    SciTech Connect

    Yogesh K. Vohra

    2005-05-12

    The focus of this program at the University of Alabama at Birmingham (UAB) is to develop the next generation of designer diamond anvils that can perform simultaneous joule heating and temperature profile measurements in a diamond anvil cell. A series of tungsten-rhenium thermocouples will be fabricated onto to the anvil and encapsulated by a chemical vapor deposited diamond layer to allow for a complete temperature profile measurement across the anvil. The tip of the diamond anvil will be engineered to reduce the thermal conductivity so that the tungsten-heating coils can be deposited on top of this layer. Several different approaches will be investigated to engineer the tip of the diamond anvil for reduction in thermal conductivity (a) isotopic mixture of 12C and 13C in the diamond layer, (b) doping of diamond with impurities (nitrogen and/or boron), and (c) growing diamond in a higher concentration of methane in hydrogen plasma. Under this academic alliance with Lawrence Livermore National Laboratory (LLNL), PI and his graduate students will use the lithographic and diamond polishing facility at LLNL. This proposed next generation of designer diamond anvils will allow multi-tasking capability with the ability to measure electrical, magnetic, structural and thermal data on actinide materials with unparallel sensitivity in support of the stockpile stewardship program.

  15. Retention time prediction in temperature-programmed, comprehensive two-dimensional gas chromatography: modeling and error assessment.

    PubMed

    Barcaru, Andrei; Anroedh-Sampat, Andjoe; Janssen, Hans-Gerd; Vivó-Truyols, Gabriel

    2014-11-14

    In this paper we present a model relating experimental factors (column lengths, diameters and thickness, modulation times, pressures and temperature programs) with retention times. Unfortunately, an analytical solution to calculate the retention in temperature programmed GC × GC is impossible, making thus necessary to perform a numerical integration. In this paper we present a computational physical model of GC × GC, capable of predicting with a high accuracy retention times in both dimensions. Once fitted (e.g., calibrated), the model is used to make predictions, which are always subject to error. In this way, the prediction can result rather in a probability distribution of (predicted) retention times than in a fixed (most likely) value. One of the most common problems that can occur when fitting unknown parameters using experimental data is overfitting. In order to detect overfitting situations and assess the error, the K-fold cross-validation technique was applied. Another technique of error assessment proposed in this article is the use of error propagation using Jacobians. This method is based on estimation of the accuracy of the model by the partial derivatives of the retention time prediction with respect to the fitted parameters (in this case entropy and enthalpy for each component) in a set of given conditions. By treating the predictions of the model in terms of intervals rather than as precise values, it is possible to considerably increase the robustness of any optimization algorithm. PMID:25441353

  16. Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

    SciTech Connect

    Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel; Borek, Theodore Thaddeus, III

    2010-09-01

    Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.

  17. LASER DESORPTION IONIZATION OF SIZE RESOLVED LIQUID MICRODROPLETS. (R823980)

    EPA Science Inventory

    Mass spectra of single micrometer-size glycerol droplets containing organic and inorganic analytes were obtained by on-line laser desorption ionization. Aerosol droplets entered the mass spectrometer through an inlet where they were detected by light scattering of a continuous la...

  18. One-dimensional steam flow in porous media under desorption

    SciTech Connect

    Cuong Phu Nghiem; Ramey, Henry J., Jr.

    1991-01-01

    Performance forecasting for a hypothetical field with Geysers greywacke rock is performed to demonstrate the importance of desorption effect, the actual adsorption isotherm was found to be well approximated by the Langmuir equation. Results obtained suggest that adsorption is the dominant mechanism for steam in geothermal reservoirs.

  19. Sorption-desorption of aminocyclopyrachlor in selected Brazilian soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aminocyclopyrachlor sorption and desorption was investigated in 14 soils from Brazil, representing a range of pH, and organic carbon (OC) and clay contents. Sorption kinetics demonstrated that soil-solution equilibrium was attained in a 24-h period. Freundlich equation adequately described behavior ...

  20. Desorption electrospray ionization-mass spectrometry of proteins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization-mass spectrometry (DESI-MS) was evaluated for the detection of proteins ranging in molecular mass from 12 to 66 kDa. Proteins were uniformly deposited on a solid surface without pretreatment and analyzed with a DESI source coupled to a quadrupole ion trap mass spec...

  1. SITE TECHNOLOGY CAPSULE: CLEAN BERKSHIRES, INC. - THERMAL DESORPTION SYSTEM

    EPA Science Inventory

    The thermal desorption process devised by Clean Berkshires, Inc., works by vaporizing the organic contaminants from the soil with heat, isolating the contaminant! in a gas stream, and then destroying them in a high efficiency afterburner. he processed solids are either replaced f...

  2. Site technology capsule: Clean Berkshires, Inc. thermal desorption system

    SciTech Connect

    Not Available

    1994-08-01

    The thermal desorption process devised by Clean Berkshires Inc. (CBI) uses standard rotary kiln technology to remove organic contaminants from excavated solid wastes. The process works by vaporizing and isolating the constituents in a gas stream and then destroying them in a high-efficiency afterburner. The processed solids are either reused or disposed of as nonhazardous, depending on applicable regulations.

  3. SITE TECHNOLOGY CAPSULE: CLEAN BERKSHIRES, INC. THERMAL DESORPTION SYSTEM

    EPA Science Inventory

    The thermal desorption process devised by Clean Berkshires, Inc., works by vaporizing the organic contaminants from the soil with heat, isolating the contaminant! in a gas stream, and then destroying them in a high efficiency afterburner. The processed solids are either replaced ...

  4. Thermal desorption behavior of helium in aged titanium tritide films

    NASA Astrophysics Data System (ADS)

    Cheng, G. J.; Shi, L. Q.; Zhou, X. S.; Liang, J. H.; Wang, W. D.; Long, X. G.; Yang, B. F.; Peng, S. M.

    2015-11-01

    The desorption behavior of helium in TiT(1.5∼1.8)-x3Hex film samples (x = 0.0022-0.22) was investigated by thermal desorption technique in vacuum condition in this paper. The thermal helium desorption spectrometry (THDS) of aging titanium tritide films prepared by electron beam evaporation revealed that, depending on the decayed 3He concentration in the samples, there are more than four states of helium existing in the films. The divided four zones in THDS based on helium states represent respectively: (1) the mobile single helium atoms with low activation energy in all aging samples resulted from the interstitial sites or dissociated from interstitial clusters, loops and dislocations, (2) helium bubbles inside the grain lattices, (3) helium bubbles in the grain boundaries and interconnected networks of dislocations in the helium concentration of 3Hegen/Ti > 0.0094, and (4) helium bubbles near or linked to the film surface by interconnected channel for later aging stage with 3Hegen/Ti > 0.18. The proportion of helium desorption in each zone was estimated, and dissociated energies of helium for different trapping states were given.

  5. Dust as interstellar catalyst. I. Quantifying the chemical desorption process

    NASA Astrophysics Data System (ADS)

    Minissale, M.; Dulieu, F.; Cazaux, S.; Hocuk, S.

    2016-01-01

    Context. The presence of dust in the interstellar medium has profound consequences on the chemical composition of regions where stars are forming. Recent observations show that many species formed onto dust are populating the gas phase, especially in cold environments where UV- and cosmic-ray-induced photons do not account for such processes. Aims: The aim of this paper is to understand and quantify the process that releases solid species into the gas phase, the so-called chemical desorption process, so that an explicit formula can be derived that can be included in astrochemical models. Methods: We present a collection of experimental results of more than ten reactive systems. For each reaction, different substrates such as oxidized graphite and compact amorphous water ice were used. We derived a formula for reproducing the efficiencies of the chemical desorption process that considers the equipartition of the energy of newly formed products, followed by classical bounce on the surface. In part II of this study we extend these results to astrophysical conditions. Results: The equipartition of energy correctly describes the chemical desorption process on bare surfaces. On icy surfaces, the chemical desorption process is much less efficient, and a better description of the interaction with the surface is still needed. Conclusions: We show that the mechanism that directly transforms solid species into gas phase species is efficient for many reactions.

  6. Quantitative matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Roder, Heinrich; Hunsucker, Stephen W.

    2008-01-01

    This review summarizes the essential characteristics of matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOF MS), especially as they relate to its applications in quantitative analysis. Approaches to quantification by MALDI-TOF MS are presented and published applications are critically reviewed. PMID:19106161

  7. Desorption of Arsenic from Drinking Water Distribution System Solids

    EPA Science Inventory

    Given the limited knowledge regarding the soluble release of arsenic from DWDS solids, the objectives of this research were to: 1) investigate the effect of pH on the dissolution/desorption of arsenic from DWDS solids, and 2) examine the effect of orthophosphate on the soluble re...

  8. INITIAL SCREENING OF THERMAL DESORPTION FOR SOIL REMEDIATION

    EPA Science Inventory

    The purpose of this paper is to present procedures for collecting and evaluating key data that affect the potential application of thermal desorption for a specific site. hese data are defined as "critical success factors". he screening procedure can be used to perform an initial...

  9. INITIAL SCREENING OF THERMAL DESORPTION FOR SOIL REMEDIATION

    EPA Science Inventory

    The purpose of the paper is to present procedures for collecting and evaluating key data that affect the potential application of thermal desorption for a specific site. These data are defined as 'criticalsuccess factors'. The screening prodcedure can be used to peerform an ini...

  10. Sorption-desorption of indaziflam in selected agricultural soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sorption and desorption of indaziflam in 6 soils from Brazil and 3 soils from the USA, with different physical chemical properties, were investigated using the batch equilibration method. Sorption kinetics demonstrated that soil-solution equilibrium was attained in a 24-h period. The Freundlich equa...

  11. LASER DESORPTION IONIZATION OF ULTRAFINE AEROSOL PARTICLES. (R823980)

    EPA Science Inventory

    On-line analysis of ultrafine aerosol particle in the 12 to 150 nm size range is performed by
    laser desorption/ionization. Particles are size selected with a differential mobility analyzer and then
    sent into a linear time-of-flight mass spectrometer where they are ablated w...

  12. Desorption electrospray ionization mass spectrometry of intact bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization (DESI) mass spectrometry (MS) was used to differentiate 7 bacterial species based on their measured DESI-mass spectral profile. Both Gram positive and Gram negative bacteria were tested and included Escherichia coli, Staphyloccocus aureus, Enterococcus sp., Bordete...

  13. DEMONSTRATION BULLETIN: THERMAL DESORPTION SYSTEM - CLEAN BERKSHIRES, INC.

    EPA Science Inventory

    A thermal desorption system (TDS) has been developed by Clean Berkshires, Inc. (CBI), Lanesboro, Massachusetts for ex-situ treatment of soils and other media contaminated with organic pollutants. The TDS uses heat as both a physical separation mechanism and as a means to destro...

  14. Water absorption and desorption in shuttle ablator and insulation materials

    NASA Technical Reports Server (NTRS)

    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.

  15. Improving low temperature properties of synthetic diesel fuels derived from oil shale. Alternative fuels utilization program

    SciTech Connect

    Frankenfeld, J.W.; Taylor, W.F.

    1980-11-01

    The ability of additives to improve the cold flow properties of shale oil derived fuels boiling in the diesel fuel range was evaluated. Because a commercial shale oil industry did not exist to provide actual samples of finished fuels, a representative range of hydroprocessed shale oil fractions was prepared for use in the additive testing work. Crude oil shale from Occidental Shale Company was fractionated to give three liquids in the diesel fuel boiling range. The initial boiling point in each case was 325/sup 0/F (163/sup 0/C). The final boiling points were 640/sup 0/F (338/sup 0/C), 670/sup 0/F (354/sup 0/C) and 700/sup 0/F (371/sup 0/F). Each fraction was hydrotreated to three different severities (800, 1200 and 1500 psi total pressure) over a Shell 324 nickel molybdate on alumina catalyst at 710 to 750/sup 0/F to afford 9 different model fuels. A variety of commercial and experimental additives were evaluated as cold flow improvers in the model fuels at treat levels of 0.04 to 0.4 wt %. Both the standard pour point test (ASTM D97) and a more severe low temperature flow test (LTFT) were employed. Reductions in pour points of up to 70/sup 0/F and improvements in LTFT temperatures up to 16/sup 0/F were achieved. It is concluded that flow improver additives can play an important role in improving the cold flow properties of future synthetic fuels of the diesel type derived from oil shale.

  16. USING METHANOL-WATER SYSTEMS TO INVESTIGATE PHENANTHRENE SORPTION-DESORPTION ON SEDIMENT

    EPA Science Inventory

    Sorption isotherm nonlinearity, sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic matter (NOM) polymers associated with soils and sediments. A conceptualizat...

  17. Thermal Desorption Kinetics of Volatiles on Silicate ``Smokes:'' Analog to Micrometeoric Impact Vapor Condensates

    NASA Astrophysics Data System (ADS)

    McLain, J. L.; Sarantos, M.; Johnson, N. M.; Keller, J. W.; Nuth, J. A.; Farrell, W. M.

    2015-11-01

    Laboratory measurements of the thermal desorption kinetics of Ar, H2O and other common lunar volatiles on silicate smokes will be presented, with a focus on comparing the desorption energies and surface chemistry with other regolith analogs.

  18. Investigations into ultraviolet matrix-assisted laser desorption

    SciTech Connect

    Heise, T.W.

    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/cm{sup 2}. 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.

  19. Concentration-dependent kinetics of pollutant desorption from soils.

    PubMed

    Braida, Washington J; White, Jason C; Zhao, Dongye; Ferrandino, Francis J; Pignatello, Joseph J

    2002-12-01

    Sorption-desorption kinetics play a major role in transport and bioavailability of pollutants in soils. Contaminant concentration is a potentially important factor controlling kinetics. A previous paper dealt with the effect of solute concentration on fractional uptake rates of phenanthrene and pyrene from a finite aqueous source. In this study we determined the effect of initial phenanthrene sorbed concentration (q(0)) on the fractional mass desorption rates from each of six soils to a zero-concentration solution, approximated by including a polymer adsorbent (Tenax) as a third-phase sink. The soils were preequilibrated with phenanthrene for 180 d. Consistent with theory, the fractional desorption rates determined by empirical curve fitting increased with q(0) provided the isotherm was nonlinear. After 500 to 600 d of desorption at the steepest possible concentration gradient, all soils retained a highly resistant fraction, which ranged from 4 to 31% of q(0), except for one soil at a high q(0). The highly resistant fraction decreased with increasing q(0), for nonlinear isotherm cases, but increased with q(0) for linear or nearly linear isotherm cases. Application of a nonlinear diffusion model, the dual-mode diffusion model (DMDM), to the nonresistant fraction gave reasonably good fits. The DMDM attributes the increase with concentration of the apparent diffusivity to a decrease in the proportion of sorbate occupying immobile sites (holes) in soil organic matter. The concentration-dependent term in the expression for the apparent diffusivity correlated with either of two indices that reflect the linearity of the sorption isotherm. Bunker C oil present in one soil acted as a partition domain. The findings of this study are consistent with heterogeneous models of soil organic matter, and indicate that concentration effects should be taken into account whenever desorption rate is important. PMID:12463551

  20. A low-power pressure-and temperature-programmed separation system for a micro gas chromatograph.

    SciTech Connect

    Sacks, Richard D. (University of Michigan, Ann Arbor, MI); Robinson, Alex Lockwood (Advanced Sensor Technologies, Albuquerque, NM); Lambertus, Gordon R. (University of Michigan, Ann Arbor, MI); Potkay, Joseph A. (University of Michigan, Ann Arbor, MI); Wise, Kensall D. (University of Michigan, Ann Arbor, MI)

    2006-10-01

    This thesis presents the theory, design, fabrication and testing of the microvalves and columns necessary in a pressure- and temperature-programmed micro gas chromatograph ({micro}GC). Two microcolumn designs are investigated: a bonded Si-glass column having a rectangular cross section and a vapor-deposited silicon oxynitride (Sion) column having a roughly circular cross section. Both microcolumns contain integrated heaters and sensors for rapid, controlled heating. The 3.2 cm x 3.2 cm, 3 m-long silicon-glass column, coated with a non-polar polydimethylsiloxane (PDMS) stationary phase, separates 30 volatile organic compounds (VOCs) in less than 6 min. This is the most efficient micromachined column reported to date, producing greater than 4000 plates/m. The 2.7 mm x 1.4 mm Sion column eliminates the glass sealing plate and silicon substrate using deposited dielectrics and is the lowest power and fastest GC column reported to date; it requires only 11 mW to raise the column temperature by 100 C and has a response time of 11s and natural temperature ramp rate of 580 C/min. A 1 m-long PDMS-coated Sion microcolumn separates 10 VOCs in 52s. A system-based design approach was used for both columns.

  1. Catalytic membrane program novation: High temperature catalytic membrane reactors. Final report

    SciTech Connect

    Kleiner, R.N.

    1998-08-28

    The original objective was to develop an energy-efficient hydrocarbon dehydrogenation process based on catalytic membrane reactors. Golden Technologies determined that the goals of this contract would be best served by novating the contract to an end user or other interested party which is better informed on the economic justification aspects of petrochemical refining processes to carry out the remaining work. In light of the Chevron results, the program objective was broadened to include development of inorganic membranes for applications in the chemical industry. The proposed membrane technologies shall offer the potential to improve chemical production processes via conversion increase and energy savings. The objective of this subcontract is to seek a party that would serve as a prime contractor to carry out the remaining tasks on the agreement and bring the agreement to a successful conclusion. Four tasks were defined to select the prime contractor. They were (1) prepare a request for proposal, (2) solicit companies as potential prime contractors as well as team members, (3) discuss modifications requested by the potential prime contractors, and (4) obtain, review and rank the proposals. The accomplishments on the tasks is described in detail in the following sections.

  2. Multiple sample characterization of coals and other substances by controlled-atmosphere programmed temperature oxidation

    DOEpatents

    LaCount, Robert B.

    1993-01-01

    A furnace with two hot zones holds multiple analysis tubes. Each tube has a separable sample-packing section positioned in the first hot zone and a catalyst-packing section positioned in the second hot zone. A mass flow controller is connected to an inlet of each sample tube, and gas is supplied to the mass flow controller. Oxygen is supplied through a mass flow controller to each tube to either or both of an inlet of the first tube and an intermediate portion between the tube sections to intermingle with and oxidize the entrained gases evolved from the sample. Oxidation of those gases is completed in the catalyst in each second tube section. A thermocouple within a sample reduces furnace temperature when an exothermic condition is sensed within the sample. Oxidized gases flow from outlets of the tubes to individual gas cells. The cells are sequentially aligned with an infrared detector, which senses the composition and quantities of the gas components. Each elongated cell is tapered inward toward the center from cell windows at the ends. Volume is reduced from a conventional cell, while permitting maximum interaction of gas with the light beam. Reduced volume and angulation of the cell inlets provide rapid purgings of the cell, providing shorter cycles between detections. For coal and other high molecular weight samples, from 50% to 100% oxygen is introduced to the tubes.

  3. Computer program MCAP-TOSS calculates steady-state fluid dynamics of coolant in parallel channels and temperature distribution in surrounding heat-generating solid

    NASA Technical Reports Server (NTRS)

    Lee, A. Y.

    1967-01-01

    Computer program calculates the steady state fluid distribution, temperature rise, and pressure drop of a coolant, the material temperature distribution of a heat generating solid, and the heat flux distributions at the fluid-solid interfaces. It performs the necessary iterations automatically within the computer, in one machine run.

  4. Application of acid-activated Bauxsol for wastewater treatment with high phosphate concentration: Characterization, adsorption optimization, and desorption behaviors.

    PubMed

    Ye, Jie; Cong, Xiangna; Zhang, Panyue; Zeng, Guangming; Hoffmann, Erhard; Liu, Yang; Wu, Yan; Zhang, Haibo; Fang, Wei; Hahn, Hermann H

    2016-02-01

    Acid-activated Bauxsol was applied to treat wastewater with high phosphate concentration in a batch adsorption system in this paper. The effect of acid activation on the change of Bauxsol structure was systematically investigated. The mineralogical inhomogeneity and intensity of Bauxsol decreased after acid activation, and FeCl3·2H2O and Al(OH)3 became the dominant phases of acid-activated Bauxsol adsorption. Moreover, the BET surface area and total pore volume of Bauxsol increased after acid activation. Interaction of initial solution pH and adsorption temperature on phosphate adsorption onto acid-activated Bauxsol was investigated by using response surface methodology with central composite design. The maximum phosphate adsorption capacity of 192.94 mg g(-1) was achieved with an initial solution pH of 4.19 and an adsorption temperature of 52.18 °C, which increased by 7.61 times compared with that of Bauxsol (22.40 mg g(-1)), and was higher than other adsorbents. Furthermore, the desorption studies demonstrated that the acid-activated Bauxsol was successfully regenerated with 0.5 mol L(-1) HCl solution. The adsorption capacity and desorption efficiency of acid-activated Bauxsol maintained at 80.48% and 93.02% in the fifth adsorption-desorption cycle, respectively, suggesting that the acid-activated Bauxsol could be repeatedly used in wastewater treatment with high phosphate concentration. PMID:26606195

  5. Sorption and desorption characteristics of a packed bed of clay-CaCl{sub 2} desiccant particles

    SciTech Connect

    Tretiak, C.S.; Abdallah, N. Ben

    2009-10-15

    Desiccants can be used in conjunction with solar energy to provide a viable alternative to traditional air conditioning techniques. A desiccant consisting of clay and calcium chloride was developed and tested using multiple sorption and desorption cycles. During sorption, inlet air temperatures from 23 to 36 C with corresponding relative humidities of 42-66% were tested. Additionally, superficial air velocities from 0.17 to 0.85 m/s were tested. During desorption, inlet air temperatures from 50 to 57 C and superficial air velocities of approximately 0.30 and 0.60 m/s were tested. A regression equation was determined for the mass of water sorbed by the clay-CaCl2 desiccant with a R{sup 2} value of 0.917. The desorption data was regressed to an exponential function and significant k-values were determined. An equation for pressure drop through the desiccant was determined and compared to existing models. The desiccant was found to perform well during the repeated test cycles though small masses of desiccant were lost due to surface disintegration of the desiccant spheres. (author)

  6. Mechanisms of H2O desorption from amorphous solid water by 157-nm irradiation: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    DeSimone, Alice J.; Crowell, Vernon D.; Sherrill, C. David; Orlando, Thomas M.

    2013-10-01

    The photodesorption of water molecules from amorphous solid water (ASW) by 157-nm irradiation has been examined using resonance-enhanced multiphoton ionization. The rotational temperature has been determined, by comparison with simulations, to be 425 75 K. The time-of-flight spectrum of H2O (v = 0) has been fit with a Maxwell-Boltzmann distribution with a translational temperature of 700 200 K (0.12 0.03 eV). H+ and OH+ fragment ions have been detected with non-resonant multiphoton ionization, indicating vibrationally excited parent water molecules with translational energies of 0.24 0.08 eV. The cross section for water removal from ASW by 7.9-eV photons near 100 K is (6.9 1.8) 10-20 cm2 for >10 L H2O exposure. Electronic structure computations have also probed the excited states of water and the mechanisms of desorption. Calculated electron attachment and detachment densities show that exciton delocalization leads to a dipole reversal state in the first singlet excited state of a model system of hexagonal water ice. Ab Initio Molecular Dynamics simulations show possible desorption of a photo-excited water molecule from this cluster, though the non-hydrogen bonded OH bond is stretched significantly before desorption. Potential energy curves of this OH stretch in the electronic excited state show a barrier to dissociation, lending credence to the dipole reversal mechanism.

  7. High-temperature-staged fluidized-bed combustion (HITS), bench scale experimental test program conducted during 1980. Final report

    SciTech Connect

    Anderson, R E; Jassowski, D M; Newton, R A; Rudnicki, M L

    1981-04-01

    An experimental program was conducted to evaluate the process feasibility of the first stage of the HITS two-stage coal combustion system. Tests were run in a small (12-in. ID) fluidized bed facility at the Energy Engineering Laboratory, Aerojet Energy Conversion Company, Sacramento, California. The first stage reactor was run with low (0.70%) and high (4.06%) sulfur coals with ash fusion temperatures of 2450/sup 0/ and 2220/sup 0/F, respectively. Limestone was used to scavenge the sulfur. The produced low-Btu gas was burned in a combustor. Bed temperature and inlet gas percent oxygen were varied in the course of testing. Key results are summarized as follows: the process was stable and readily controllable, and generated a free-flowing char product using coals with low (2220/sup 0/F) and high (2450/sup 0/F) ash fusion temperatures at bed temperatures of at least 1700/sup 0/ and 1800/sup 0/F, respectively; the gaseous product was found to have a total heating value of about 120 Btu/SCF at 1350/sup 0/F, and the practicality of cleaning the hot product gas and delivering it to the combustor was demonstrated; sulfur capture efficiencies above 80% were demonstrated for both low and high sulfur coals with a calcium/sulfur mole ratio of approximately two; gasification rates of about 5,000 SCF/ft/sup 2/-hr were obtained for coal input rates ranging from 40 to 135 lbm/hr, as required to maintain the desired bed temperatures; and the gaseous product yielded combustion temperatures in excess of 3000/sup 0/F when burned with preheated (900/sup 0/F) air. The above test results support the promise of the HITS system to provide a practical means of converting high sulfur coal to a clean gas for industrial applications. Sulfur capture, gas heating value, and gas production rate are all in the range required for an effective system. Planning is underway for additional testing of the system in the 12-in. fluid bed facility, including demonstration of the second stage char burnup reactor.

  8. Spreading of lithium on a stainless steel surface at room temperature

    NASA Astrophysics Data System (ADS)

    Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

    2016-01-01

    Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. The spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62?m/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500K (Edes=1.54eV), sub-monolayer Li desorption occurred in a TPD peak at 942K (Edes=2.52eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium-lithium bonding.

  9. Detection of trace ink compounds in erased handwritings using electrospray-assisted laser desorption ionization mass spectrometry.

    PubMed

    Kao, Yi-Ying; Cheng, Sy-Chyi; Cheng, Chu-Nian; Shiea, Jentaie; Ho, Hsiu-O

    2014-06-01

    Writings made with erasable pens on paper surfaces can either be rubbed off with an eraser or rendered invisible by changing the temperature of the ink. However, trace ink compounds still remain in the paper fibers even after rubbing or rendering. The detection of these ink compounds from erased handwritings will be helpful in knowing the written history of the paper. In this study, electrospray-assisted laser desorption ionization/mass spectrometry was used to characterize trace ink compounds remaining in visible and invisible ink lines. The ink compounds were desorbed from the paper surface by irradiating the handwritings with a pulsed laser beam; the desorbed analytes were subsequently ionized in an electrospray plume and detected by a quadrupole time-of-flight mass spectrometry mass analyzer. Because of the high spatial resolution of the laser beam, electrospray-assisted laser desorption ionization/mass spectrometry analysis resulted in minimal damage to the sample documents. PMID:24913397

  10. Study of the temperature-programmed reaction synthesis of early transition metal carbide and nitride catalyst materials from oxide precursors

    SciTech Connect

    Claridge, J.B.; York, A.P.E.; Brungs, A.J.; Green, M.L.H.

    2000-01-01

    The synthesis of high surface area carbide and nitride materials from binary and ternary oxides of vanadium, niobium, tantalum, molybdenum, and tungsten, suitable for use as catalysts for a wide range of reactions, has been investigated via the temperature-programmed reaction (TPRe) method, in various gas mixtures. TPRe of oxides in CH{sub 4}/H{sub 2}, C{sub 2}H{sub 6}/H{sub 2}, or NH{sub 3} yield materials with surface areas > 40 m{sup 2}/g. For the reaction with ethane or ammonia the reaction appears to proceed topotactically while that with methane does not; however, the conversion of nitrides to carbides in CH{sub 4}/H{sub 2} does appear to proceed topotactically.

  11. Development of Designer Diamond Technology for High Pressure High Temperature Experiments in Support of Stockpile Stewardship Program

    SciTech Connect

    Vohra, Yogesh, K.

    2009-10-28

    The role of nitrogen in the fabrication of designer diamond was systematically investigated by adding controlled amount of nitrogen in hydrogen/methane/oxygen plasma. This has led to a successful recipe for reproducible fabrication of designer diamond anvils for high-pressure high-temperature research in support of stockpile stewardship program. In the three-year support period, several designer diamonds fabricated with this new growth chemistry were utilized in high-pressure experiments at UAB and Lawrence Livermore National Laboratory. The designer diamond anvils were utilized in high-pressure studies on heavy rare earth metals, high pressure melting studies on metals, and electrical resistance measurements on iron-based layered superconductors under high pressures. The growth chemistry developed under NNSA support can be adapted for commercial production of designer diamonds.

  12. Adsorption and desorption of Cd(II) onto titanate nanotubes and efficient regeneration of tubular structures.

    PubMed

    Wang, Ting; Liu, Wen; Xu, Nan; Ni, Jinren

    2013-04-15

    Efficient regeneration of desorbed titanate nanotubes (TNTs) was investigated with cycled Cd(II) adsorption and desorption processes. After desorption of Cd (II) from TNTs using 0.1M HNO3, regeneration could be simply achieved with only 0.2M NaOH at ambient temperature, i.e. 2% of the NaOH needed for virgin TNTs preparation at 130C. The regenerated TNTs displayed similar adsorption capacity of Cd(II) even after six recycles, while significant reduction could be detected for desorbed TNTs without regeneration. The virgin TNTs, absorbed TNTs, desorbed TNTs and regenerated TNTs were systematically characterized. As results, the ion-exchange mechanism with Na(+) in TNTs was convinced with obvious change of -TiO(ONa)2 by FTIR spectroscopy. The easy recovery of the damaged tubular structures proved by TEM and XRD was ascribed to asymmetric distribution of H(+) and Na(+) on the surface side and interlayer region of TNTs. More importantly, the cost-effective regeneration was found possibly related to complex form of TNTs-OCd(+)OH(-) onto the adsorbed TNTs, which was identified with help of X-ray photoelectron spectroscopy, and further indicated due to high relevance to an unexpected mole ratio of 1:1 between exchanged Na(+) and absorbed Cd(II). PMID:23500417

  13. Laser desorption mass spectrometry and small angle neutron scattering of heavy fossil materials

    SciTech Connect

    Hunt, J.E.; Winans, R.E.; Thiyagarajan, P.

    1997-09-01

    The determination of the structural building blocks and the molecular weight range of heavy hydrocarbon materials is of crucial importance in research on their reactivity and for their processing. The chemically and physically heterogenous nature of heavy hydrocarbon materials, such as coals, heavy petroleum fractions, and residues, dictates that their structure and reactivity patterns be complicated. The problem is further complicated by the fact that the molecular structure and molecular weight distribution of these materials is not dependent on a single molecule, but on a complex mixture of molecules which vary among coals and heavy petroleum samples. Laser Desorption mass spectrometry (LDMS) is emerging as a technique for molecular weight determination having found widespread use in biological polymer research, but is still a relatively new technique in the fossil fuel area. Small angle neutron scattering (SANS) provides information on the size and shape of heavy fossil materials. SANS offers the advantages of high penetration power even in thick cells at high temperatures and high contrast for hydrocarbon systems dispersed in deuterated solvents. LDMS coupled with time of flight has the advantages of high sensitivity and transmission and high mass range. We have used LDMS to examine various heavy fossil-derived materials including: long chain hydrocarbons, asphaltenes from petroleum vacuum resids, and coals. This paper describes the application of laser desorption and small angle neutron scattering techniques to the analysis of components in coals, petroleum resids and unsaturated polymers.

  14. Comparison of three plasma sources for ambient desorption/ionization mass spectrometry.

    PubMed

    McKay, Kirsty; Salter, Tara L; Bowfield, Andrew; Walsh, James L; Gilmore, Ian S; Bradley, James W

    2014-09-01

    Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources. PMID:24894843

  15. Adsorption / Desorption Behavior of Water Vapor in an Adsorbent Desiccant Rotor

    NASA Astrophysics Data System (ADS)

    Tsujiguchi, Takuya; Kodama, Akio

    Adsorption / desorption behavior of water vapor onto desiccant rotor has been investigated to improve the desiccant cooling system by means of computer simulation. In this paper, we paid attention to the relationship between the equilibrium amount of water adsorbed onto the desiccant material and the relative humidity, that is adsorption isotherm as a principal characteristic feature of adsorbent. Considering actual adsorbents, five types of adsorption isotherms were assumed to clarify the influence of adsorption isotherm on the dehumidifying performance. After the investigation on the influences of some operating conditions on the dehumidifying performance at each selected adsorption isotherm, it was found that higher dehumidifying performance and reduction of length of desiccant rotor could be achieved by selecting appropriate adsorption isotherm. It was also predicted that S-shaped adsorption isotherm which is raised sharply at relative humidity around 15 % could produce the lowest air humidity at regeneration air temperature 80 C. Moreover influence of the intraparticle diffusion coefficient which significantly influence on the adsorption / desorption rate was discussed choosing two adsorption isotherm from the above five isotherms. It seems that effective range of the intraparticle diffusion coefficient for the significant improvement of the dehumidifying performance was strongly influenced by the shape of adsorption isotherm.

  16. Diffusion barriers in the kinetics of water vapor adsorption/desorption on activated carbons

    SciTech Connect

    Harding, A.W.; Foley, N.J.; Thomas, K.M.; Norman, P.R.; Francis, D.C.

    1998-07-07

    The adsorption of water vapor on a highly microporous coconut-shell-derived carbon and a mesoporous wood-derived carbon was studied. These carbons were chosen as they had markedly different porous structures. The adsorption and desorption characteristics of water vapor on the activated carbons were investigated over the relative pressure range p/p{degree} = 0--0.9 for temperatures in the range 285--313 K in a static water vapor system. The adsorption isotherms were analyzed using the Dubinin-Serpinski equation, and this provided an assessment of the polarity of the carbons. The kinetics of water vapor adsorption and desorption were studied with different amounts of preadsorbed water for set changes in pressure relative to the saturated vapor pressure (p/p{degree}). The adsorption kinetics for each relative pressure step were compared and used to calculate the activation energies for the vapor pressure increments. The kinetic results are discussed in relation to their relative position on the equilibrium isotherm and the adsorption mechanism of water vapor on activated carbons.

  17. Bulk Diffusion-Controlled Thermal Desorption Spectroscopy with Examples for Hydrogen in Iron

    NASA Astrophysics Data System (ADS)

    Kirchheim, Reiner

    2015-11-01

    Bulk diffusion-controlled thermal desorption spectroscopy (TDS) is studied by solving the corresponding transport equations numerically as well as analytically with appropriate approximations. The two solutions are compared in order to validate the derived equations including the Kissinger equation. Besides the diffusion of the desorbed species through the sample, trapping of the species at special lattice sites within the sample is included in the numerical and approximate analytical solutions. Trapping energies are mono-energetic, multi-energetic, or are described by a box-type distribution. TDS-peaks were simulated for different heating rates, sample thicknesses, trap concentrations, and initial degrees of trap saturation. It is shown that for the case of mono-energetic traps, Kissinger's equation is obeyed for both numerical and analytical results. This widely used equation for reaction rate-controlled studies is derived in an explicit form for diffusion-controlled processes. Together with a newly derived relation between maximum desorption rate and temperature, TDS-spectra yield information about diffusion coefficient, trap energies, and trap concentration as well as trap saturation. This is exemplified using data of two experimental studies. Although the numerical and analytical treatment is in general applicable to all diffusion species, hydrogen in iron alloys is used as a model system because of its technological importance and the increasing number of experimental work with this material.

  18. Microwave-induced plasma desorption/ionization source for ambient mass spectrometry.

    PubMed

    Zhan, Xuefang; Zhao, Zhongjun; Yuan, Xin; Wang, Qihui; Li, Dandan; Xie, Hong; Li, Xuemei; Zhou, Meigui; Duan, Yixiang

    2013-05-01

    A new ionization source based on microwave induced plasma was developed for ambient desorption/ionization. The microwave-induced plasma desorption/ionization source (MIPDI) was composed of a copper Surfatron microwave cavity where a fused-silica tube was centered axially. Stable nonlocal thermodynamic equilibrium plasma was generated in the quartz discharge tube when a microwave at a frequency of 2450 MHz was coupled to the microwave cavity. Analytes deposited on the surface of poly(tetrafluoroethylene) (PTFE) or quartz slide after hydrofluoric acid (HF) etching were desorbed and ionized by the plasma. The performance of the MIPDI technique was validated by the analysis of a variety of chemical substances, polymer compounds, and pharmaceutical drugs using argon or helium as the discharge gas. Protonated [M + H](+) or deprotonated [M - H](-) ions were observed in the positive or negative mode. MIPDI was also used for the analysis of compounds in a complex matrix without any sample preparation. MIPDI was also capable of analyzing liquid samples. The signal-to-noise ratio was 463 in the analysis of 9.2 ng of phenylalanine, and the limit of detection was 60 pg for phenylalanine. MIPDI could desorb and ionize analytes with a molecular weight of up to 1200, which was demonstrated by the analysis of polyethylene glycol 800 (PEG800). MIPDI has advantages of simple instrumentation, relatively high temperature, stability, and reproducibility. PMID:23534913

  19. Visualization and Measurement of Adsorption/Desorption Process of Ethanol in Activated Carbon Adsorber

    NASA Astrophysics Data System (ADS)

    Asano, Hitoshi; Murata, Kenta; Takenaka, Nobuyuki; Saito, Yasushi

    Adsorption refrigerator is one of the efficient tools for waste heat recovery, because the system is driven by heat at relative low temperature. However, the coefficient of performance is low due to its batch operation and the heat capacity of the adsorber. In order to improve the performance, it is important to optimize the configuration to minimize the amount of driving heat, and to clarify adsorption/desorption phenomena in transient conditions. Neutron radiography was applied to visualize and measure the adsorption amount distribution in an adsorber. The visualization experiments had been performed at the neutron radiography facility of E-2 port of Kyoto University Research Reactor. Activated carbon and ethanol were used as the adsorbent and refrigerant. From the acquired radiographs, adsorption amount was quantitatively measured by applying the umbra method using a checkered neutron absorber with boron powder. Then, transient adsorption and desorption processes of a rectangular adsorber with 84 mm in width, 50 mm in height and 20 mm in depth were visualized. As the result, the effect of fins in the adsorbent layer on the adsorption amount distribution was clearly visualized.

  20. Improvement in hydrogen desorption from ?- and ?-MgH2 upon transition-metal doping.

    PubMed

    Hussain, Tanveer; Maark, Tuhina Adit; Chakraborty, Sudip; Ahuja, Rajeev

    2015-08-24

    A thorough study of the structural, electronic, and hydrogen-desorption properties of ?- and ?-MgH2 phases substituted by selected transition metals (TMs) is performed through first-principles calculations based on density functional theory (DFT). The TMs considered herein include Sc, V, Fe, Co, Ni, Cu, Y, Zr, and Nb, which substitute for Mg at a doping concentration of 3.125?% in both the hydrides. This insertion of TMs causes a variation in the cell volumes of ?- and ?-MgH2 . The majority of the TM dopants decrease the lattice constants, with Ni resulting in the largest reduction. From the formation-energy calculations, it is predicted that except for Cu and Ni, the mixing of all the selected TM dopants with the MgH2 phases is exothermic. The selected TMs also influence the stability of both ?- and ?-MgH2 and cause destabilization by weakening the Mg?H bonds. Our results show that doping with certain TMs can facilitate desorption of hydrogen from ?- and ?-MgH2 at much lower temperatures than from their pure forms. The hydrogen adsorption strengths are also studied by density-of-states analysis. PMID:26079892