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Sample records for temperature programmed desorption

  1. A dynamic calibration technique for temperature programmed desorption spectroscopy.

    PubMed

    Hurst, K E; Heben, M J; Blackburn, J L; Gennett, T; Dillon, A C; Parilla, P A

    2013-02-01

    A novel, rapid and accurate calibration procedure as a means for quantitative gas desorption measurement by temperature programmed desorption (TPD) spectroscopy is presented. Quantitative measurement beyond the linear regime of the instrument is achieved by associating an instantaneous calibrated molar flow rate of gas to the detector response. This technique is based on fundamental methods, and is independently verified by comparison to the hydrogen desorption capacity of a known standard metal hydride with known stoichiometry. The TPD calibration procedure described here may be used for any pure gas, and the accuracy is demonstrated for the specific case of hydrogen. PMID:23464247

  2. 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.

  3. 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.

  4. 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 |JΩM>=|{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.

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

    DOEpatents

    Linker, Kevin L.; Bouchier, Frank A.; Theisen, Lisa; Arakaki, Lester H.

    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.

  6. 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.

  7. 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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

  10. 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

  11. The dissociation kinetics of NO on Rh(111) as studied by temperature programmed static secondary ion mass spectrometry and desorption

    NASA Astrophysics Data System (ADS)

    Borg, H. J.; Reijerse, J. F. C.-J. M.; van Santen, R. A.; Niemantsverdriet, J. W.

    1994-12-01

    Temperature programmed static secondary ion mass spectrometry (TPSSIMS) and temperature programmed desorption (TPD) have been used to study the kinetics of adsorption, dissociation, and desorption of NO on Rh(111). At 100 K, NO adsorption is molecular and proceeds via mobile precursor state kinetics with a high initial sticking probability. SSIMS indicates the presence of two distinct NO adsorption states, indicative of threefold adsorption at low coverage, and occupation of bridge sites at higher coverages. Three characteristic coverage regimes appear with respect to NO dissociation. At low coverages θNO<0.25 ML, NO dissociates completely at temperatures between 275 and 340 K. If we neglect lateral interactions and assume pure first order dissociation kinetics, we find effective values for the activation barrier and preexponential factor of 40±6 kJ/mol and 106±1 s-1 for the dissociation of 0.15-0.20 ML NO. However, if we assume that a NO molecule needs an ensemble of three to four vacant sites in order to dissociate, the preexponential factor and activation energy are ˜1011 s-1 and 65 kJ/mol, in better agreement with transition state theory expectations. The Nads and Oads dissociation products desorb as N2 and O2, respectively, with desorption parameters Edes=118±10 kJ/mol and νdes=1010.1±1.0 s-1 for N2 in the zero coverage limit. At higher coverages, the desorption kinetics of N2 is strongly influenced by the presence of coadsorbed oxygen. In the medium coverage range 0.25<θNO<0.50 ML, part of the NO desorbs molecularly, with an estimated desorption barrier of 113±10 kJ/mol and a preexponential of 1013.5±1.0 s-1. Dissociation of NO becomes progressively inhibited due to site blocking, the onset shifting from 275 K at 0.25 ML to 400 K, coinciding with the NO desorption temperature, at a coverage of 0.50 ML. The accumulation of nitrogen and oxygen atoms on the highly covered surface causes a destabilization of the nitrogen atoms, which results in an additional low-temperature desorption state for N2. For high initial NO coverages above 0.50 ML, the dissociation is completely self-inhibited, indicating that all sites required for dissociation are blocked. The desorption of the more weakly bound—presumably bridged—NO does not generate the sites required for dissociation; these become only available after the desorption of—presumably triply coordinated—NO.

  12. Adsorption and desorption of dibenzothiophene on Ag-titania studied by the complementary temperature-programmed XPS and ESR

    NASA Astrophysics Data System (ADS)

    Samokhvalov, Alexander; Duin, Evert C.; Nair, Sachin; Tatarchuk, Bruce J.

    2011-02-01

    Adsorption, desorption and structure of the surface chemical compounds formed upon interaction of dibenzothiophene (DBT) in solution of n-octane with the sulfur-selective Ag/Titania sorbent for the ultradeep desulfurization of liquid fuels was characterized by the temperature-programmed X-ray photoemission spectroscopy (XPS) and Electron Spin Resonance. Adsorption of DBT proceeds via chemisorption via the oxygen-containing surface groups. Desorption of DBT and thermal regeneration of the “spent” Ag/Titania were studied by the complementary temperature-programmed XPS and ESR from 25 °C to 525 °C, in the high vacuum vs. air. The XPS spectrum of the pure DBT is reported for the first time.

  13. Study of temperature-programmed desorption of tert-butylamine to measure the surface acidity of solid catalysts

    SciTech Connect

    Aguayo, A.T.; Arandes, J.M.; Olazar, M.; Bilbao, J. )

    1991-08-01

    In this paper, the technique of temperature-programmed desorption of tert-butylamine is described to measure the surface acidity of solid catalysts. The use of this base has advantages over the use of ammonia, pyridine, and n-butylamine. The desorption measurement is carried out by two methods, gas chromatography and thermogravimetry, and the advised conditions are described for both methods. Catalysts of SiO{sub 2}/Al{sub 2}O{sub 3}, bifunctionals of Ni-SiO{sub 2}/Al{sub 2}O{sub 3}, and a commercial cracking zeolite have been studied. A comparison of the desorption results with those of the other acidity measurement techniques (such as titration with n-butylamine in the liquid phase and kinetic measurement of isomerization of n-butenes as the test reaction) allows the acidity measured with tert-butylamine desorption to be classified as strong, corresponding to the active sites in most of the reactions among the hydrocarbon compounds catalyzed by acids.

  14. 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

  15. Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1×1

    DOE PAGESBeta

    Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; Kay, Bruce D.; Kim, Yu Kwon

    2016-02-24

    In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction productmore » desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

  16. Temperature Programmed Desorption of Quench-condensed Krypton and Acetone in Air; Selective Concentration of Ultra-trace Gas Components.

    PubMed

    Suzuki, Taku T; Sakaguchi, Isao

    2016-01-01

    Selective concentration of ultra-trace components in air-like gases has an important application in analyzing volatile organic compounds in the gas. In the present study, we examined quench-condensation of the sample gas on a ZnO substrate below 50 K followed by temperature programmed desorption (TPD) (low temperature TPD) as a selective gas concentration technique. We studied two specific gases in the normal air; krypton as an inert gas and acetone as a reactive gas. We evaluated the relationship between the operating condition of low temperature TPD and the lowest detection limit. In the case of krypton, we observed the selective concentration by exposing at 6 K followed by thermal desorption at about 60 K. On the other hand, no selectivity appeared for acetone although trace acetone was successfully concentrated. This is likely due to the solvent effect by a major component in the air, which is suggested to be water. We suggest that pre-condensation to remove the water component may improve the selectivity in the trace acetone analysis by low temperature TPD. PMID:27063719

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

    PubMed

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

    2016-01-01

    In order to understand the interactions between beta-hexachlorocyclohexane (HCH) and chemical groups at activated carbon (AC) surface, the solid samples were hydrogenated aiming to decrease the amounts of oxygenated groups. Two AC samples designated by BagH2O and BagP1.5 were prepared by water vapor activation and phosphoric acid activation, respectively, of sugarcane bagasse used as an AC precursor. A more simple molecule 1,2,3-trichloropropane (TCP) is used as a model of chlorinated compound. The AC were characterized by infrared, X-ray photoelectron spectroscopy (XPS), Raman resonance spectroscopies, as well as temperature-programmed desorption coupled with mass spectrometry (TPD-MS). BagP1.5 and BagH2O AC surface contained oxygenated groups. Upon hydrogenation, a decrease of most of these group amxounts was observed for both samples, while hydroxyl groups increased. On the basis of temperature-programmed desorption data obtained for AC samples contaminated with TCP or HCH, it was possible to determine the type of hydrogen bond formed between each AC and HCH. PMID:26018287

  18. Quantitative detection of trace explosive vapors by programmed temperature desorption gas chromatography-electron capture detector.

    PubMed

    Field, Christopher R; Lubrano, Adam; Woytowitz, Morgan; Giordano, Braden C; Rose-Pehrsson, Susan L

    2014-01-01

    The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e., samples collected on vapor collection tubes and standards prepared in solution vials. Additionally, the method can account for instrumentation losses, which makes it ideal for minimizing variability and quantitative trace chemical detection. Gas chromatography with an electron capture detector is an instrumentation configuration sensitive to nitro-energetics, such as TNT and RDX, due to their relatively high electron affinity. However, vapor quantitation of these compounds is difficult without viable vapor standards. Thus, we eliminate the requirement for vapor standards by combining the sensitivity of the instrumentation with a direct liquid deposition protocol to analyze trace explosive vapor samples. PMID:25145416

  19. 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

  20. Dosimeter-type NOx sensing properties of KMnO4 and its electrical conductivity during temperature programmed desorption.

    PubMed

    Groß, 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

  1. 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

  2. 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}.

  3. 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.

  4. Study of the adsorption reactions of thiophene on Cu(I)/HY-Al2O3 by Fourier transform infrared and temperature-programmed desorption: adsorption, desorption, and sorbent regeneration mechanisms.

    PubMed

    Tang, Xiao-Lin; Shi, Li

    2011-10-01

    This work mainly involved the investigation of the adsorption of thiophene on Cu(I)-supported HY-Al(2)O(3). It demonstrated a high sulfur capacity of 10 mg sulfur/g sorbent when the HY/Al(2)O(3) mass ratio was 3, loaded with 12% copper, calcined at 550 °C, and tested at ambient temperature. In situ Fourier transform infrared (FTIR) and temperature-programmed desorption (TPD) results indicated that the adsorption mechanisms on Cu(I)/HY-Al(2)O(3) primarily were π-complexation and sulfur-adsorbent (S-M; σ) bonds. Pyridine-FTIR showed the total weak Lewis acid contribution to the Cu(I)/HY-Al(2)O(3) adsorption desulfurization performance. PMID:21870798

  5. 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

  6. 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.

  7. 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.

  8. Optical detection of CO and CO2 temperature dependent desorption from carbon nanotube clusters.

    PubMed

    Chistiakova, M V; Armani, A M

    2014-10-01

    The development of new materials relies on high precision methods to quantify adsorption/desorption of gases from surfaces. One commonly used approach is temperature programmed desorption spectroscopy. While this approach is very accurate, it requires complex instrumentation, and it is limited to performing experiments under high vacuum, thus restricting experimental scope. An alternative approach is to integrate the surface of interest directly onto a detector face, creating an active substrate. One surface that has applications in numerous areas is the carbon nanotube (CNT). As such, an active substrate that integrates a CNT surface on a sensor and is able to perform measurements in ambient environments will have significant impact. In the present work, we have developed an active substrate that combines an optical sensor with a CNT cluster substrate. The optical sensor is able to accurately probe the temperature dependent desorption of carbon monoxide and carbon dioxide gases from the CNT cluster surface. This active substrate will enable a wide range of temperature dependent desorption measurements to be performed from a scientifically interesting material system. PMID:25189292

  9. 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

  10. Apparatus for low temperature thermal desorption spectroscopy of portable samples.

    PubMed

    Stuckenholz, S; Büchner, C; Ronneburg, H; Thielsch, G; Heyde, M; Freund, H-J

    2016-04-01

    An experimental setup for low temperature thermal desorption spectroscopy (TDS) integrated in an ultrahigh vacuum-chamber housing a high-end scanning probe microscope for comprehensive multi-tool surface science analysis is described. This setup enables the characterization with TDS at low temperatures (T > 22 K) of portable sample designs, as is the case for scanning probe optimized setups or high-throughput experiments. This combination of techniques allows a direct correlation between surface morphology, local spectroscopy, and reactivity of model catalysts. The performance of the multi-tool setup is illustrated by measurements of a model catalyst. TDS of CO from Mo(001) and from Mo(001) supported MgO thin films were carried out and combined with scanning tunneling microscopy measurements. PMID:27131703

  11. Apparatus for low temperature thermal desorption spectroscopy of portable samples

    NASA Astrophysics Data System (ADS)

    Stuckenholz, S.; Büchner, C.; Ronneburg, H.; Thielsch, G.; Heyde, M.; Freund, H.-J.

    2016-04-01

    An experimental setup for low temperature thermal desorption spectroscopy (TDS) integrated in an ultrahigh vacuum-chamber housing a high-end scanning probe microscope for comprehensive multi-tool surface science analysis is described. This setup enables the characterization with TDS at low temperatures (T > 22 K) of portable sample designs, as is the case for scanning probe optimized setups or high-throughput experiments. This combination of techniques allows a direct correlation between surface morphology, local spectroscopy, and reactivity of model catalysts. The performance of the multi-tool setup is illustrated by measurements of a model catalyst. TDS of CO from Mo(001) and from Mo(001) supported MgO thin films were carried out and combined with scanning tunneling microscopy measurements.

  12. 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.

  13. Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH{sub 3} and CO{sub 2}

    SciTech Connect

    Kustrowski, Piotr; Chmielarz, Lucjan; Bozek, Ewa; Sawalha, Murad; Roessner, Frank

    2004-02-02

    Mg-Al hydrotalcites intercalated with five different interlayer anions--CO{sub 3}{sup 2-}, SO{sub 4}{sup 2-}, Cl{sup -}, HPO{sub 4}{sup 2-} or terephthalate--were synthesized by either the coprecipitation or ion-exchange method. The structure of the as-synthesized samples and the presence of intended anions in the interlayer gallery of hydrotalcites were determined by X-ray diffraction and FTIR spectroscopy. On calcination at 600 deg. C the materials were transformed into mixed metal oxides. The kind of the counterbalancing anions present in the parent hydrotalcite influences strongly textural parameters of the obtained Mg-Al oxides. Both temperature-programmed desorption of NH{sub 3} and CO{sub 2}, and test reaction of 2-methyl-3-butyn-2-ol (MBOH) conversion were used to determine the acidity and basicity of the samples. The hydrotalcite derived mixed Mg-Al oxides showed the presence of Broensted and Lewis acid and base sites. However, the strong basic character of the solids caused that acetone and acetylene were observed as the major products of MBOH conversion.

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

    DOE PAGESBeta

    Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

    2016-03-24

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

  16. Low-temperature plasma probe for ambient desorption ionization.

    PubMed

    Harper, Jason D; Charipar, Nicholas A; Mulligan, Christopher C; Zhang, Xinrong; Cooks, R Graham; Ouyang, Zheng

    2008-12-01

    A low-temperature plasma (LTP) probe has been developed for ambient desorption ionization. An ac electric field is used to induce a dielectric barrier discharge through use of a specially designed electrode configuration. The low-temperature plasma is extracted from the probe where it interacts directly with the sample being analyzed, desorbing and ionizing surface molecules in the ambient environment. This allows experiments to be performed without damage to the sample or underlying substrate and, in the case of biological analysis on skin surfaces, without electrical shock or perceptible heating. Positive or negative ions are produced from a wide range of chemical compounds in the pure stateand as mixtures in the gaseous, solution, or condensed phases, using He, Ar, N2, or ambient air as the discharge gas. Limited fragmentation occurs, although it is greater in the cases of the molecular than the atomic discharge gases. The effectiveness of the LTP probe has been demonstrated by recording characteristic mass spectra and tandem mass spectra of samples containing hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) from poly(tetrafluoroethylene) (PTFE) surfaces where limits of detection are as low as 5 pg. Other performance characteristics, when using a commercial ion trap mass spectrometer, include 3-4 orders of magnitude linear dynamic range in favorable cases. Demonstration applications include direct analysis of cocaine from human skin, determination of active ingredients directly in drug tablets, and analysis of toxic and therapeutic compounds in complex biological samples. Ionization of chemicals directly from bulk aqueous solution has been demonstrated, where limits of detection are as low as 1 ppb. Large surface area sampling and control of fragmentation by a simple adjustment of the electrode configuration during operation are other demonstrated characteristics of the method. PMID:19551980

  17. 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.

  18. Desorption of cadmium from goethite: effects of pH, temperature and aging.

    PubMed

    Mustafa, Ghulam; Kookana, Rai S; Singh, Balwant

    2006-07-01

    Cadmium is perhaps environmentally the most significant heavy metal in soils. Bioavailability, remobilization and fate of Cd entering in soils are usually controlled by adsorption-desorption reactions on Fe oxides. Adsorption of Cd on soil colloids including Fe oxides has been extensively studied but Cd desorption from such soil minerals has received relatively little attention. Some factors that affect Cd adsorption on goethite include pH, temperature, aging, type of index cations, Cd concentrations, solution ionic strength and presence of organic and inorganic ions. This research was conducted to study the influence of pH, temperature and aging on Cd desorption from goethite. Batch experiments were conducted to evaluate Cd desorption from goethite with 0.01 M Ca(NO3)2. In these experiments Cd desorption was observed at 20, 40 and 70 degrees C in combination with aging for 16 h, 30, 90 and 180 d from goethite that adsorbed Cd from solutions containing initial Cd concentrations of 20, 80 and 180 microM. Following the adsorption step Cd desorption was measured by 15 successive desorptions after aging at various temperatures. At the lowest amount of initially adsorbed Cd and equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 17% with aging from 16 h to 180 d and the corresponding decrease at equilibrium pH 6.0 was from 32% to 3%. There was a substantial decrease in Cd desorption with increasing equilibration temperature. For example, in goethite with the lowest amount of initial adsorption at equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 31% with increase in temperature from 20 to 70 degrees C, even after 16 h. Dissolution of Cd adsorbed goethite in 1M HCl, after 15 successive desorptions with 0.01 M Ca(NO3)2, indicated that approximately 60% of the Cd was surface adsorbed. Overall, dissolution kinetics data revealed that 23% to 88% Cd could not be desorbed, which could possibly be diffused into the cracks and got entrapped in goethite crystals. At elevated temperature increased equilibrium solution pH favoured the formation of CaCO3 and CdCO3 which reasonably decreased Cd desorption. Cadmium speciation showed the formation of calcite and otavite minerals at 40 and 70 degrees C due to increase in pH (>9.5) during aging. X-ray diffraction analysis (XRD) of these samples also revealed the formation of CaCO3 at elevated temperatures with aging. While mechanisms such as Cd diffusion and/or entrapment into fissures and cracks in goethite structure with increase in temperature and aging are possible. PMID:16330070

  19. 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

  20. 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...

  1. 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. ...

  2. 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. ...

  3. ON-SITE ENGINEERING REPORT FOR THE LOW-TEMPERATURE THERMAL DESORPTION PILOT-SCALE TEST ON CONTAMINATED SOIL

    EPA Science Inventory

    Performance of the thermal desorption process for removal of organic contaminants, mostly polynuclear aromatic hydrocarbons (PAHs), from soils was evaluated. The Superfund Site soil tested was a fine sandy soil contaminated with creosote. An optimum operating temperature of 550 C...

  4. 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.

  5. Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1979-01-01

    Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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...

  11. NaAlH4 Mixed with Carbon Nanotubes, Fullerene, and Titanium to Yield the Lowest Temperature for Hydrogen Desorption

    NASA Astrophysics Data System (ADS)

    Hildebrand, Jennifer; McFadden, Patrick; Kim, Sanga; Dobbins, Tabbetha

    Recent research in hydrogen storage has improved dehydrogenation methods with solid-state compounds. NaAlH4 is a complex hydrides which release hydrogen at a lower temperature making the compound a great candidate for hydrogen storage. However, a catalyst should be combined with NaAlH4 to release the lowest desorption temperature. Prior research showed that interaction of NaAlH4 with nanotube or fullerene effectively weakens the Al-H bonds causing hydrogen desorption at lower temperatures. In the present study, NaAlH4 is ball milled with three of these catalysts: titanium, carbon nanotubes and fullerene and the milling time is varied from 10 to 30 minutes to compare the dehydrogenation rates in each setup. The phase structures were identified using the X-ray diffraction. Of these catalysts, the fullerene yielded the most interesting result showing nanostructuring of the hydride during ball milling. The possibility of ``shot peening'' of the NaAlH4 by the fullerenes is explored.

  12. 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

  13. On-site engineering report for the low-temperature thermal-desorption pilot-scale test on contaminated soil

    SciTech Connect

    Smith, M.L.; Groen, A.; Hessling, J.; Alperin, E.

    1992-07-01

    Performance of the thermal desorption process for removal of organic contaminants, mostly polynuclear aromatic hydrocarbons (PAHs), from soils was evaluated. The Superfund Site soil tested was a fine sandy soil contaminated with creosote. An optimum operating temperature of 550 C and an optimum operating residence time of 10 min, determined from bench studies, were used in the pilot-scale desorber. Contaminants removed from the soil were captured or destroyed in the associated air pollution control equipment. Test results showed that greater than 99% of the PAHs were removed from the soil. The concentration of total PAHs averaged 4629 mg/Kg in the pretreated soils and were below detection in the posttreated soils.

  14. 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.

  15. 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.

  16. Waste/Rock Interactions Technology Program: the status of radionuclide sorption-desorption studies performed by the WRIT program

    SciTech Connect

    Serne, R.J.; Relyea, J.F.

    1982-04-01

    The most credible means for radionuclides disposed as solid wastes in deep-geologic repositories to reach the biosphere is through dissolution of the solid waste and subsequent radionuclide transport by circulating ground water. Thus safety assessment activities must consider the physicochemical interactions between radionculides present in ground water with package components, rocks and sediments since these processes can significantly delay or constrain the mass transport of radionuclides in comparison to ground-water movement. This paper focuses on interactions between dissolved radiouclides in ground water and rocks and sediments away from the near-field repository. The primary mechanism discussed is adsorption-desorption, which has been studied using two approaches. Empirical studies of adsorption-desorption rely on distribution coefficient measurements while mechanism studies strive to identify, differentiate and quantify the processes that control nuclide retardation.

  17. 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

  18. 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

  19. Laser-induced thermal desorption of aniline from silica surfaces

    NASA Astrophysics Data System (ADS)

    Voumard, Pierre; Zenobi, Renato

    1995-10-01

    A complete study on the energy partitioning upon laser-induced thermal desorption of aniline from silica surfaces was undertaken. The measurements include characterization of the aniline-quartz adsorption system using temperature-programmed desorption, the extrapolation of quasiequilibrium desorption temperatures to the regime of laser heating rates on the order of 109-1010 K/s by computational means, measurement of the kinetic energy distributions of desorbing aniline using a pump-probe method, and the determination of internal energies with resonance-enhanced multiphoton ionization spectroscopy. The measurements are compared to calculations of the surface temperature rise and the resulting desorption rates, based on a finite-difference mathematical description of pulsed laser heating. While the surface temperature of laser-heated silica reaches about 600-700 K at the time of desorption, the translational temperature of laser-desorbed aniline was measured to be Tkin=420±60 K, Tvib was 360±60 K, and Trot was 350±100 K. These results are discussed using different models for laser-induced thermal desorption from surfaces.

  20. Thermal decomposition pathway and desorption study of isopropanol and tert-butanol on Si(100)

    NASA Astrophysics Data System (ADS)

    Kim, Jaehyun; Kim, Kwansoo; Yong, Kijung

    2002-09-01

    Thermal decomposition pathway and desorption of isopropanol (IPA) and tert-butanol on Si(100) were studied using temperature programed desorption. Adsorbed alcohols studied were decomposed into atomic hydrogen and alkoxy on the surface. During heating the sample up to 1000 K, acetone, propylene, and hydrogen were desorbed as decomposition products of IPA on Si(100). Desorption pathways of IPA on Si(100) were largely consistent with those on metal surfaces: beta-hydride elimination reaction to acetone and C-O scission to propylene. For tert-butanol, which has no beta-hydrogen, isobutene and hydrogen were observed as main desorption products. copyright 2002 American Vacuum Society.

  1. 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.

  2. 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)

  3. 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+δ) (LSM) and La(0.60) Sr(0.40) Fe(0.80) Mn(0.20) O(3-δ) (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

  4. 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

  5. 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 μm), 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.

  6. 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.

  7. 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...

  8. 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.

  9. Kinetic plots for programmed temperature gas chromatography.

    PubMed

    Jespers, Sander; Roeleveld, Kevin; Lynen, Frederic; Broeckhoven, Ken; Desmet, Gert

    2016-06-10

    The applicability of the kinetic plot theory to temperature-programmed gas chromatography (GC) has been confirmed experimentally by measuring the efficiency of a temperature gradient separation of a simple test mixture on 15, 30, 60 and 120m long (coupled) columns. It has been shown that the temperature-dependent data needed for the kinetic plot calculation can be obtained from isothermal experiments at the significant temperature, a temperature that characterizes the entire gradient run. Furthermore, optimal flow rates have been calculated for various combinations of column length, diameter, and operating temperature (or significant temperature). The tabulated outcome of these calculations provide good starting points for the optimization of any GC separation. PMID:27179678

  10. 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.

  11. Isomer-Selective Detection of Aromatic Molecules in Temperature-Programmed Desorption for Model Catalysis.

    PubMed

    Winbauer, Andreas; Kollmannsberger, Sebastian L; Walenta, Constantin A; Schreiber, Patrick; Kiermaier, Josef; Tschurl, Martin; Heiz, Ueli

    2016-05-17

    Based on three different molecules dosed on a Pt(111) single crystal the selectivity and sensitivity of REMPI-TPD in UHV is investigated for a potential application in heterogeneous catalysis. It is shown that the two structural isomers ethylbenzene and p-xylene can be discriminated by REMPI in a standard TPD experiment. The latter is not possible for the ionization with electrons in a Q-MS. It is further demonstrated by benzene TPD studies that the sensitivity of the REMPI-TOF-MS is comparable to commercial EI-Q-MS solutions and enables the detection of less than 0.6% molecules of a monolayer. PMID:27078611

  12. 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.

  13. 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.

  14. 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)

  15. 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.

  16. 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 1°C/s, the main feature peaks at ˜410°C while the smaller feature occurs as a shoulder near 320°C. 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 400°C. 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.)

  17. 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.

  18. Evidence for non-hydrogen desorption limited growth of Si from disilane at very low temperatures in gas source molecular beam epitaxy?

    NASA Astrophysics Data System (ADS)

    Werner, K.; Butzke, S.; Radelaar, S.; Balk, P.

    1994-03-01

    We have studied the growth of Si from disilane on Si(001) in gas source molecular beam epitaxy (GSMBE). The growth rates were measured in situ from reflection high energy electron diffraction (RHEED) intensity oscillations. Various experiments at different substrate temperature and disilane fluxes were carried out. At low temperatures the rate limiting step during the deposition of Si from disilane is the desorption of hydrogen from the Si surface. The hydrogen stems from the dissociation of the disilane molecule and ties up surface dangling bonds, which in turn block adsorption sites for incoming disilane molecules. Therefore, when measuring the growth rate at a given temperature against the supplied disilane flux, one expects to observe saturation of the rate for high absolute surface hydrogen coverages (θ ∗≈1). This behaviour was indeed found. Interestingly, even at growth temperatures as low as 468°C, the growth rate still increases slightly with increasing flux. According to the literature, at such low temperatures, the steady state absolute surface hydrogen coverage is already larger than 1 for the applied fluxed. It has been suggested that an additional reaction path for the growth from disilane on hydrogen terminated surfaces must exist, albeit that it contributes only weakly to the overall growth rate. For example, a possible alternative reaction path, proposed by Kulkarni et al. for the decomposition of disilane on a Si(111) surface: Si 2H 6(g)+H(s)→SiH 4(g)+SiH 3(s), could occur for Si(001) as well (s and g denote species at the surface and in the gas phase, respectively). However, it will be shown in this paper that an additional reaction mechanism is not at all necessary to describe the growth rate dependence on the flux even at low temperatures.

  19. Temperature measurements during the CAMP program. [Cold Arctic Mesopause Program

    NASA Technical Reports Server (NTRS)

    Philbrick, C. R.; Barnett, J.; Gerndt, R.; Offermann, D.; Pendleton, W. R., Jr.; Schlyter, P.; Witt, G.; Schmidlin, J. F.

    1984-01-01

    The Cold Arctic Mesopause Program (CAMP) was conducted at ESRANGE, Sweden, in July/August 1982. During the time period of several weeks, the temperature was monitored by ground-based OH emission spectrometers and by satellite radiance measurements. Rocket launchings occurred on the nights of 3/4 and 11/12 August. On 3/4 August, seven rocket payloads were launched during a period of noctilucent cloud sighting over ESRANGE. The presence of the NLC was confirmed by several rocket-borne photometer profiles. The temperature measurements showed that the temperature profiles in the stratosphere and lower mesosphere were near the expected values of high latitude summer models. A large amplitude wave structure with three temperature minima of 139K, 114K and 111K were observed at altitudes between 83 and 94 km. The temperature minimum at 83 km was the location of the observed NLC. The temperature minima caused by the growth of the gravity wave amplitude in the highly stable mesosphere provide the regions for the growth of particles by nucleation to optical scattering size, as well as regions where the nuclei for condensation can be formed through ion chemistry paths.

  20. 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.

  1. Influence of temperature and atmosphere on polychlorinated dibenzo-p-dioxins and dibenzofurans desorption from waste incineration fly ash.

    PubMed

    Yang, Jie; Yan, Mi; Li, Xiaodong; Chen, Tong; Lu, Shengyong; Yan, Jianhua; Buekens, Alfons

    2015-01-01

    A fly ash sample was heated for 1 h to 200°C, 300°C and 400°C, in order to study the influence of temperature and gas phase composition on the removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from fly ash derived from municipal solid waste incineration. The tests were conducted by treating a fixed bed of fly ash both in an inert (nitrogen) and in a reducing (nitrogen+hydrogen) gas flow in a horizontal bench-scale quartz tubular reactor, heated by a surrounding tubular furnace. The results indicate that most of the PCDD/Fs in fly ash were removed by thermal treatment, especially when the temperature was higher than 300°C: the PCDD/Fs' removal efficiency attained up to 96%. PCDD/Fs dechlorination and destruction were much more important than PCDD/Fs desorption, under either inert or reducing atmosphere. At 200°C and 300°C, the experiments with reducing atmosphere yielded slightly better results than those in nitrogen; yet, this tendency was reversed at 400°C. In general, both treatment modes can fully meet the requirements regarding the concentration of dioxins in fly ash to be sent for landfill in China. PMID:25241904

  2. 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.

  3. The kinetics and energetics of polymer desorption from surfaces

    NASA Astrophysics Data System (ADS)

    Paserba, Kris Robert

    The dynamics of polymer desorption from solid surfaces have been studied by measuring the desorption kinetics of long-chain oligomers from the surface of single crystalline graphite. Desorption rates have been measured using temperature programmed desorption (TPD) for a series of oligomeric n-alkanes [CNH2 N+2, N = 5 to 60], poly(ethylene glycol) dimethyl ethers [CH3(OCH2CH2) nOCH3, n = 1 to 22], and poly(ethylene glycols) [H(OCH2CH2)nOH, n = 1 to 20] from a graphite surface. Desorption is observed to occur molecularly in all cases through a first-order process with a desorption barrier, DE‡des , that is roughly independent of the oligomer chain length, N (where N = 3n + 3 for the polyethers). The pre-exponential factors, nu, of the desorption reaction in all cases were found to be independent of the oligomer chain length and substantially greater than kBT/h ≈ 10 13 s-1 with average values on the order of nu avg ≈ 1019 s-1. More interesting is the fact that the dependence of the DE‡des on N is non-linear over the range of chain lengths explored for each series of oligomers and the relationship between these two quantities can be expressed as DE‡des = A + BNgamma, where the exponent assumes a value of gamma ≈ 0.50 in each case. This non-linear behavior reveals some aspect of the complex process or mechanism by which oligomeric species desorb from surfaces. We have attempted to explain the origin of the non-linear dependence of the DE‡des on chain length for each set of adsorbates through a model that uses transition state theory as the basis for describing the desorption rate constant. More important is the fact that our model provides an extremely good quantitative fit to the observed dependence of the DE‡des on N for each group of adsorbates. The results of our modeling reveal conclusively for the first time that conformational isomerism plays a significant role in determining the desorption kinetics of oligomers from surfaces.

  4. 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-).

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. 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...

  10. 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.

  11. 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.

  12. 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.

  13. 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. ...

  14. 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.

  15. 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.

  16. Finite difference program for calculating hydride bed wall temperature profiles

    SciTech Connect

    Klein, J.E.

    1992-10-29

    A QuickBASIC finite difference program was written for calculating one dimensional temperature profiles in up to two media with flat, cylindrical, or spherical geometries. The development of the program was motivated by the need to calculate maximum temperature differences across the walls of the Tritium metal hydrides beds for thermal fatigue analysis. The purpose of this report is to document the equations and the computer program used to calculate transient wall temperatures in stainless steel hydride vessels. The development of the computer code was motivated by the need to calculate maximum temperature differences across the walls of the hydrides beds in the Tritium Facility for thermal fatigue analysis.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. First-principles study of water desorption from montmorillonite surface.

    PubMed

    Zhang, Yao; Meng, Yingfeng; Liu, Houbin; Yang, Mingli

    2016-05-01

    Knowledge about water desorption is important to give a full picture of water diffusion in montmorillonites (MMT), which is a driving factor in MMT swelling. The desorption paths and energetics of water molecules from the surface of MMT with trapped Li(+), Na(+) or K(+) counterions were studied using periodic density functional theory calculations. Two paths-surface and vacuum desorption-were designed for water desorption starting from a stationary structure in which water bonds with both the counterion and the MMT surface. Surface desorption is energetically more favorable than vacuum desorption due to water-surface hydrogen bonds that help stabilize the intermediate structure of water released from the counterion. The energy barriers of water desorption are in the order of Li(+) > Na(+) > K(+), which can be attributed to the short ionic radius of Li(+), which favors strong binding with the water molecule. The temperature dependence of water adsorption and desorption rates were compared based on the computed activation energies. Our calculations reveal that the water desorption on the MMT surface has a different mechanism from water adsorption, which results from surface effects favoring stabilization of water conformers during the desorption process. PMID:27083565

  2. 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

  3. 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.

  4. Surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001)

    NASA Astrophysics Data System (ADS)

    Arena, M. V.; Westre, E. D.; George, S. M.

    1991-03-01

    The surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001) were examined using laser-induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. The surface diffusion displayed Arrhenius behavior and was coverage independent. The surface diffusion parameters for perfluoro-n-butane on Ru(001) were Edif=2.9±0.3 kcal/mol and D0=5.9×10-2±0.2 cm2/s. The desorption parameters for perfluoro-n-butane on Ru(001) were Edes=13.8±0.6 kcal/mol and νdes=2.8×1021±0.1 s-1. In comparison, the surface diffusion parameters for n-butane on Ru(001) were Edif=3.5±0.2 kcal/mol and D0=1.4×10-1±0.2 cm2/s. The desorption parameters for n-butane on Ru(001) were Edes=11.9±0.5 kcal/mol and νdes=3.6×1015±0.1 s-1. The corrugation ratio, defined as Ω≡Edif/Edes, was determined to be Ω=0.21 for perfluoro-n-butane on Ru(001). This corrugation ratio was substantially different than the corrugation ratio of Ω≊0.30 measured for n-butane and various other n-alkanes, cycloalkanes and branched alkanes on Ru(001). The comparison between perfluoro-n-butane and the other alkanes indicates that fluorination lowers the surface corrugation ratio on Ru(001). Likewise, fluorination significantly increases the preexponential for desorption from Ru(001). This study illustrates the magnitude of substituent effects on surface diffusion and desorption kinetics for a physisorbed molecule on a single-crystal metal surface.

  5. 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.

  6. 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 ...

  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. 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

  9. 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.

  10. 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...

  11. Ice in space: surface science investigations of the thermal desorption of model interstellar ices on dust grain analogue surfaces.

    PubMed

    Burke, Daren J; Brown, Wendy A

    2010-06-21

    More than 140 different molecules have been identified in the interstellar medium (ISM) to date. Dust grain particles are also found in the ISM, and some of these molecules freeze out at the cold temperatures (10-20 K) to form molecular ices. Understanding the adsorption and desorption of these ices is crucially important in understanding the processes that lead to star and planet formation, and may even help to lead to an understanding of the origin of life itself. High sensitivity surface science techniques, including temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS), are being increasingly used to investigate the interactions between dust grains and interstellar ices. This perspective provides an overview of the current level of understanding of the adsorption and desorption of astrophysically relevant molecules from a range of dust grain analogue surfaces. Whilst the focus of this review is on interstellar ices, the results discussed are equally valid to discussions of cometary and planetary ices. PMID:20520900

  12. 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.

  13. 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.

  14. 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.

    2016-05-01

    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 (reflection absorption infrared spectroscopy), and two types of mass spectroscopy protocols: temperature-programmed desorption, and during-exposure desorption 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.

  15. 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.

  16. 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.

  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. 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.

  19. Calcium lignosulfonate adsorption and desorption on Berea sandstone.

    PubMed

    Grigg, Reid B; Bai, Baojun

    2004-11-01

    This paper describes adsorption and desorption studies carried out with calcium lignosulfonate (CLS) on Berea sandstone. Circulation experiments were performed to determine CLS adsorption isotherms and the effects of CLS concentration, temperature, salinity, brine hardness, and injection rate on adsorption density. Flow-through experiments were performed to assess the reversibility of CLS adsorption and the influence of postflush rate, brine concentration, brine hardness, brine pH, and temperature on the desorption process. Results indicate that CLS adsorption isotherms on Berea sandstone follow the Freundlich isotherm law. The results presented in this paper on the effects of CLS adsorption and desorption on Berea sandstone show that: (1) increasing CLS concentration and salinity increases CLS adsorption density; (2) increasing temperature will decrease adsorption density; (3) increasing injection rate of CLS solution will slightly decrease CLS adsorption density; (4) postflush rate and salinity of brine have a large impact on the CLS desorption process; (5) the adsorption and desorption process are not completely reversible; and (5) temperature and pH of the postflush brine have little effect on desorption. PMID:15380409

  20. 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.

  1. [Desorption isotherms in amaranth flours].

    PubMed

    Alvarado, J D; Toaza, E; Coloma, G

    1990-09-01

    In milled seeds amaranth (Amaranthus hybridus) samples locally known as "ataco or sangoracha" and harvested in two consecutive years, the vapor pressure at four temperatures (15 degrees, 20 degrees, 25 degrees, 30 degrees C) was determined in samples obtained for drying in oven at different times, within a range between 60 g water/100 g dry matter for fresh seeds to 10 g water/100 g dry matter or below, as measured in a Brabender equipment. Vapor pressure of distilled water was also determined for water activity calculation. The isotherms for each temperature are presented. Application of the G.A.B. model (Guggenheim-Anderson-De Boer) allowed to establish the water content of greater stability within a range of 9.9 to 7.6 g/100 g. The third degree polynomial equations presented, adjust satisfactorily with the experimental data, and can be used to calculate equilibrium moisture content from 0.15 to 0.95 water activity values. Water desorption isotherms of foods are important to determine the equilibrium relationship between the moisture content of foods and the water activity, information which permits to establish likely physical, chemical or biological changes. It is considered that the results obtained are useful in drying, milling or storing amaranth flour. PMID:2134142

  2. 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.

  3. 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 α γ transformation related helium desorption from the γ-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.

  4. 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.

  5. 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.

  6. 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.

  7. Adsorption, Desorption, and Diffusion of Nitrogen in a Model Nanoporous Material: II. Diffusion Limited Kinetics in Amorphous Solid Water

    SciTech Connect

    Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.; Kay, Bruce D.

    2007-11-14

    Tykhon Zubkov, R. Scott Smith, Todd R. Engstrom, and Bruce D. Kay The adsorption, desorption, and diffusion kinetics of N2 on thick (up to ~9 mm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption (TPD). Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 mm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films, (>1 mm), N2 adsorption at 27 K results in a non-uniform distribution where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is ~7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Blocking adsorption sites near the film surface facilitates transport into the film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor-mediated and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed 2nd layer N2 species on top of the 1st layer chemisorbed layer.

  8. 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.

  9. Dynamic Monte-Carlo modeling of thermal desorption of H 2 from H + irradiated graphite

    NASA Astrophysics Data System (ADS)

    Liu, Shengguang; Sun, Jizhong; Dai, Shuyu; Wang, Dezhen

    2011-02-01

    Thermal desorption of hydrogen molecules from H + irradiated graphite is studied using dynamic Monte Carlo simulation. The purpose of this study is to understand the experimentally observed phenomena that the thermal desorption of H 2 from the graphite exhibits sometimes single desorption peak, sometimes double peaks, and even three desorption peaks under certain circumstances. The study result reveals that the fluence of pre-implanted H +, the concentration of trap sites, porosity, and mean crystallite volume are important parameters in determining the number of desorption peaks. It is found that low implantation fluence and high concentration of trap sites easily lead to the occurrence of single desorption peak at around 1000 K, and high implantation fluence and low concentration of trap sites favor the occurrence of double desorption peaks, with a new desorption peak at around 820 K. It is also found that small porosity of graphite and large crystallite volume benefit the occurrence of single desorption peak at around 1000 K while large porosity of graphite and small crystallite volume facilitate the occurrence of double desorption peaks, respectively, at around 820 and 1000 K. In addition, experimentally observed third desorption peak at lower temperature is reproduced by simulation with assuming the graphite containing a small concentration of solute hydrogen atoms.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  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. 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 1764±232 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.

  17. 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...

  18. Method of enhancing selective isotope desorption from metals

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. Adsorption and desorption studies of cesium on sapphire surfaces

    SciTech Connect

    Zavadil, K.R.; Ing, J.L.

    1993-12-01

    Adsorption/desorption were studied using combined surface analytical techniques. An approximate initial sticking coefficient for Cs on sapphire was measured using reflection mass spectrometry and found to be 0.9. Thermal Desorption Mass Spectrometry (TDMS) and Auger Electron Spectroscopy (AES) were used to verify that a significant decrease in sticking coefficient occurs as the Cs coverage reaches a critical submonolayer value. TDMS analysis demonstrates that Cs is stabilized on a clean sapphire surface at temperatures (1200 K) in excess of the temperatures experienced by sapphire in a TOPAZ-2 thermionic fuel element (TFE). Surface contaminants on sapphire can enhance Cs adsorption relative to the clean surface. C contamination eliminates the high temperature state of Cs desorption found on clean sapphire but shifts the bulk of the C desorption from 400 to 620 K. Surface C is a difficult contaminant to remove from sapphire, requiring annealing above 1400 K. Whether Cs is stabilized on sapphire in a TFE environment will most likely depend on relation between surface contamination and surface structure.

  5. 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.

  6. Material evaluation program, high-temperature nitriding environment

    NASA Technical Reports Server (NTRS)

    Marcy, R. D.

    1973-01-01

    Results of a program conducted to evaluate materials for construction of a space shuttle hydrazine monopropellant gas generator are presented. The program was designed to select those materials that maintain the properties of strength and ductility after exposure to an 1800 F nitriding environment for 1000 hours.

  7. 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

  8. 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 γ-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.

  9. 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.

  10. 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.

  11. 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)

  12. 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.

  13. 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).

  14. 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

  15. 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.

  16. 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.

  17. 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)

  18. Bonding configurations for nickelocene on Ag(100) and steric effects in thermal desorption

    SciTech Connect

    Borca, C.N.; Welipitiya, D.; Dowben, P.A.; Boag, N.M.

    2000-02-10

    The molecular adsorption and desorption of nickelocene, Ni(C{sub 5}H{sub 5}){sub 2}, on Ag(100) has been studied by coverage dependent angle-resolved thermal desorption. The angle-resolved thermal desorption of nickelocene is unusual in that the molecular orientation is seen to affect the angular dependence of molecular desorption. The coexistence of two chemisorption phases for molecular nickelocene adsorption on Ag(100) near the desorption temperature of approximately 230 K is identified. One phase, with the bonding configuration of the nickelocene molecular axis along the surface normal, appears to dominate at higher coverages. The results are discussed in the context of rehybridization and recent angle-resolved photoemission and high-resolution electron energy loss measurements.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. Water Vapor Desorption Characteristics of Honeycomb Type Sorption Element Composed of Organic Sorbent

    NASA Astrophysics Data System (ADS)

    Inaba, Hideo; Kida, Takahisa; Horibe, Akihiko; Kaneda, Makoto; Okamoto, Tamio; Seo, Jeong-Kyun

    This paper describes the water vapor desorption characteristics of honeycomb shape type sorbent element containing new organic sorbent of the bridged complex of sodium polyacrylate. The transient experiments in which the dry air was passed into the honeycomb type sorbent element sorbed water vapor were carried out under various conditions of air velocity, temperature, relative humidity and honeycomb length. The obtained data for desorption process were compared with those for sorption process. Finally, Sherwood number of mass transfer of the organic sorbent for desorption process was derived in terms of Reynolds number, modified Stefan number and non-dimensional honeycomb length.

  8. Adsorption and Desorption of Metallic Impurities on Si Wafer Surface in SC1 Solution

    NASA Astrophysics Data System (ADS)

    Ryuta, Jiro; Yoshimi, Toshihiro; Kondo, Hideyuki; Okuda, Hitoshi; Shimanuki, Yasushi

    1992-08-01

    Variation in the surface concentration of Fe, Ni, Cu and Zn on Si wafers due to treatment in NH4OH/H2O2/H2O solution is investigated. It is shown that adsorption and desorption of the metallic impurities occur simultaneously in the solution. The metal concentration on the wafer surface depends on the initial surface concentration, concentration in the solution, adsorption probability, desorption rate constant and the treatment time. The measured surface concentration is explained by taking into account the effects of these parameters. The variation in the desorption rate constant with the metal species, treatment temperature and the concentration in the solution is discussed.

  9. Thermal desorption of oxygen from near-stoichiometric cationic vanadium oxide clusters

    NASA Astrophysics Data System (ADS)

    Kurokawa, Hodaka; Mafuné, Fumitaka

    2016-05-01

    Oxygen desorption from cationic vanadium oxide clusters, VnOm+ (n = 2-10), composed of a near-stoichiometric (n:m = 2:5) frame with excess oxygen attached was investigated in a thermal energy region by time-of-flight mass spectrometry and thermal desorption spectrometry. Oxygen molecules were observed to desorb from the clusters during heating. The activation energy for desorption was estimated from the temperature dependence of different clusters and exhibited an even-odd alternation with respect to the cluster size, n. This alternation can be explained in terms of oxidation states of the vanadium atoms.

  10. Surface Structure Dependence in Desorption and Crystallization of Thin Interfacial Water Films on Platinum.

    PubMed

    Badan, Cansin; Heyrich, Yasmine; Koper, Marc T M; Juurlink, Ludo B F

    2016-05-01

    We study the influence of substrate structure on desorption and crystallization of water deposited at 100 K on platinum. We use ultrathin water films adsorbed to well-defined but highly corrugated Pt(211) and Pt(221) surfaces. Desorption spectra reveal variations in the wetting and subsequent layers that critically depend on step type. Crystallization is induced at much lower substrate temperatures as compared to Pt(111). The crystalline ice (CI)-like layer is also significantly more stable on stepped surfaces as evidenced by a higher desorption energy. Crystallinity of the CI-like layers is maintained over a thickness that varies strongly with step type. PMID:27093477

  11. 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.

  12. 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.

  13. Spiral Surface Growth without Desorption

    NASA Astrophysics Data System (ADS)

    Karma, Alain; Plapp, Mathis

    1998-11-01

    Spiral surface growth is well understood in the limit where the step motion is controlled by the local supersaturation of adatoms near the spiral ridge. In epitaxial thin-film growth, however, spirals can form in a step-flow regime where desorption of adatoms is negligible and the ridge dynamics is governed by the nonlocal diffusion field of adatoms on the whole surface. We investigate this limit numerically using a phase-field formulation of the Burton-Cabrera-Frank model, as well as analytically. Quantitative predictions, which differ strikingly from those of the local limit, are made for the selected step spacing as a function of the deposition flux, as well as for the dependence of the relaxation time to steady-state growth on the screw dislocation density.

  14. 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.

  15. 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,…

  16. 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.

  17. Research and development program for the development of advanced time-temperature dependent constitutive relationships. Volume 2: Programming manual

    NASA Technical Reports Server (NTRS)

    Cassenti, B. N.

    1983-01-01

    The results of a 10-month research and development program for nonlinear structural modeling with advanced time-temperature constitutive relationships are presented. The implementation of the theory in the MARC nonlinear finite element code is discussed, and instructions for the computational application of the theory are provided.

  18. 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.

  19. Dissociative and molecular adsorption and recombinative desorption of methylchlorosilanes at the Cu (001) surface

    NASA Astrophysics Data System (ADS)

    Lallo, J.; Goncharova, L. V.; Ermakov, A. V.; Hinch, B. J.; Strongin, D.

    2007-03-01

    The Direct Synthesis of dichlorodimethylsilane above Cu/Si containing surfaces, is central to the commercial manufacture of many silicone materials. The atomic scale mechanisms responsible for the high selectivity for dichlorodimethylsilane, vs. other chloromethylsilanes, is poorly understood. As part of a more extensive program we report here on the interactions of chloromethylsilanes with copper. Adsorption of dichlorodimethylsilane on Cu(001) is, at least in part, dissociative. Yet AES indicates non-stoichiometric surface concentrations of Cl and C. This observation, which is apparent in both low (140K) and room temperature exposures, is indicative of a facile recombinative desorption process. Subsequent TPD spectra also indicate the desorption of not only the parent adsorbate, but other species also. Indeed the combined cracking patterns, of simultaneously desorbing species, are inconsistent with solely (CH3)xSiCly species. We report on the TPD, AES, and high-resolution helium atom scattering studies of (i) adsorption of methylchlorosilanes, and (ii) their coadsorption with added SiH4, CH3 and Cl species, on Cu(001). Evidence for methyl cracking, and disilane production will discussed.

  20. 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.

  1. State resolved desorption measurements as a probe of surface reactions

    NASA Astrophysics Data System (ADS)

    Hodgson, A.

    2000-01-01

    Surface reactions which lead directly to gas phase products can be investigated by using state resolved techniques to measure the energy released into the newly formed molecules. This technique has been used extensively to explore oxidation of CO and the dynamics of H 2 recombinative desorption at surfaces, but so far has been applied to few other reactions. Here we review the application of final state measurements and discuss the conditions under which dynamical information can be obtained for Langmuir-Hinshelwood type surface reactions. Combining resonance enhanced multiphoton ionisation with ion time of flight detection allows translational energy distributions to be measured for a wide range of products, with full quantum state resolution. The energy release reflects scattering from a thermally populated transition state, with the recombination dynamics determining how the product state distributions depart from a thermal distribution at the surface temperature. Using the principle of detailed balance the desorption dynamics can be related to the reverse process, dissociative chemisorption. Making the link between adsorption and desorption has two benefits. Firstly, it allows us to discuss quantitatively the influence of surface temperature on the product state distributions formed by surface reactions, allowing us to avoid naive models, which treat the transition state as having a unique, well-defined energy. Secondly, the desorption results can be used to obtain relative sticking probabilities with full quantum state and translational energy resolution, providing a way to determine how internal energy influences dissociation for both hydrogen and for heavy molecules, such as nitrogen. The conditions necessary to apply detailed balance successfully are discussed and the desorption distributions expected for different types of adsorption behaviour illustrated. The recombination/dissociation dynamics of hydrogen are summarised briefly and the energy partitioning into different coordinates described. Product state measurements for some ‘heavy’ molecule reactions, such as NH 3 and NO reduction to form nitrogen and CO and H 2 oxidation are reviewed and compared to the behaviour seen for hydrogen. The desorption dynamics and the shape of the potential energy surfaces for nitrogen recombination at different metal surfaces are discussed and we suggest some future lines of development.

  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. 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

  4. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Feng, Qinzhong; Zhang, Zhiyong; Ma, Yuhui; He, Xiao; Zhao, Yuliang; Chai, Zhifang

    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 (Δ H 0 , Δ S 0 , and Δ G 0 ) 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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)

  11. Thermal Desorption Analysis of Hydrogen in High Strength Martensitic Steels

    NASA Astrophysics Data System (ADS)

    Enomoto, M.; Hirakami, D.; Tarui, T.

    2012-02-01

    Thermal desorption analyses (TDA) were conducted in high strength martensitic steels containing carbon from 0.33 to 1.0 mass pct, which were charged with hydrogen at 1223 K (950 °C) under hydrogen of one atmospheric pressure and quenched to room temperature. In 0.33C steel, which had the highest M s temperature, only one desorption peak was observed around 373 K (100 °C), whereas two peaks, one at a similar temperature and the other around and above 573 K (300 °C), were observed in the other steels, the height of the second peak increasing with carbon content. In 0.82C steel, both peaks disappeared during exposure at room temperature in 1 week, whereas the peak heights decreased gradually over 2 weeks in specimens electrolytically charged with hydrogen and aged for varying times at room temperature. From computer simulation, by means of the McNabb-Foster theory coupled with theories of carbon segregation, these peaks are likely to be due to trapping of hydrogen in the strain fields and cores of dislocations, and presumably to a lesser extent in prior austenite grain boundaries. The results also indicate that carbon atoms prevent and even expel hydrogen from trapping sites during quenching and aging in these steels.

  12. Laser-desorption mass spectrometry/mass spectrometry and the mechanism of desorption ionization

    SciTech Connect

    Zakett, D.; Schoen, A.E.; Cooks, R.G.; Hemberger, P.H.

    1981-03-11

    This paper reports sucrose mass spectra obtained by combining laser desorption with mass spectrometry/mass spectrometry. Remarkable similarities in fragmentation behavior with secondary ion mass spectra (SIMS) provide evidence for mechanistic similarities between SIMS and laser desorption (LD). Attachment of alkali metals to organic molecules (cationization) is a common feature of desorption ionization. This process also occurs during laser desorption of involatile compounds which further indicates the existence of underlying similarities between LD and SIMS. Steady ion currents (several thousand ions per laser pulse) of cationized sucrose are obtained for relatively long periods (minutes).

  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. 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.

  15. Desorption corona beam ionization source for mass spectrometry.

    PubMed

    Wang, Hua; Sun, Wenjian; Zhang, Junsheng; Yang, Xiaohui; Lin, Tao; Ding, Li

    2010-04-01

    A novel Desorption Corona Beam Ionization (DCBI) source for direct analysis of samples from surface in mass spectrometry is reported. The DCBI source can work under ambient conditions without time-consuming sample pretreatments. The source shares some common features with another ionization source - Direct Analysis in Real Time (DART), developed earlier. For example, helium was used as the discharge gas (although only corona discharge is involved in the present source), and heating of the discharge gas is required for sample desorption. However, the difference between the two sources is substantial. In the present source, a visible thin corona beam extending out around 1 cm can be formed by using a hollow needle/ring electrode structure. This feature would greatly facilitate localizing sampling areas and performing imaging/profiling experiments. The DCBI source is also capable of performing progressive temperature scans between room temperature and 450 degrees C in order to sequentially desorb samples from the surface and, therefore, to achieve a rough separation of the individual components in a complex mixture, resulting in less congestion in the mass spectrum acquired. Mass spectra for a broad range of compounds (pesticides, veterinary additives, OTC drugs, explosive materials) have been acquired using the DCBI source. For most of the compounds tested, the heater temperature required for efficient desorption is at least 150 degrees C. The molecular weight of the sample that can be desorbed/ionized is normally below 600 dalton even at the highest heater temperature, which is mainly limited by the volatility of the sample. PMID:20349536

  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. 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…

  18. 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.

  19. 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)

  20. 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.

  1. 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.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    Yakshinskiy, B. V.; Madey, T. E.

    1999-08-01

    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 formore than a few hours (refs 1-6). 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 wereport laboratory studies of photon-stimulated desorption of sodium from surfaces that simulate lunar silicates. We find that bombardment of such surfaces at temperatures of ~250K by ultraviolet photons (wavelength λ< 300nm) causes very efficient desorption of sodium atoms, induced by electronic excitations rather than by thermal processes or momentum transfer. The fluxat 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.

  4. 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

  5. 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.

  6. 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.

  7. Analytical solution and computer program (FAST) to estimate fluid fluxes from subsurface temperature profiles

    NASA Astrophysics Data System (ADS)

    Kurylyk, Barret L.; Irvine, Dylan J.

    2016-02-01

    This study details the derivation and application of a new analytical solution to the one-dimensional, transient conduction-advection equation that is applied to trace vertical subsurface fluid fluxes. The solution employs a flexible initial condition that allows for nonlinear temperature-depth profiles, providing a key improvement over most previous solutions. The boundary condition is composed of any number of superimposed step changes in surface temperature, and thus it accommodates intermittent warming and cooling periods due to long-term changes in climate or land cover. The solution is verified using an established numerical model of coupled groundwater flow and heat transport. A new computer program FAST (Flexible Analytical Solution using Temperature) is also presented to facilitate the inversion of this analytical solution to estimate vertical groundwater flow. The program requires surface temperature history (which can be estimated from historic climate data), subsurface thermal properties, a present-day temperature-depth profile, and reasonable initial conditions. FAST is written in the Python computing language and can be run using a free graphical user interface. Herein, we demonstrate the utility of the analytical solution and FAST using measured subsurface temperature and climate data from the Sendia Plain, Japan. Results from these illustrative examples highlight the influence of the chosen initial and boundary conditions on estimated vertical flow rates.

  8. Dynamics of thermal desorption of vapor from an adsorbent bed

    SciTech Connect

    Moiseichuk, O.V.; Shumyatskii, Y.I.; Suchkova, V.N.; Torocheshnikov, N.S.; Zhukova, Z.A.

    1985-09-01

    This paper establishes the profiles of the concentration and temperature waves characterizing the process of thermal desorption of vapor from an adsorbent. The experiments permit representing the process which takes place in a bed of a saturated adsorbent during thermal regeneration with a hot current. It was found that the vapor desorbed in the hot zones of the bed is repeatedly adsorbed in the cold zones. The data obtained during the experiments will apparently be useful in creating a rational quantitative model of the process of regeneration of an adsorbent by heated gas.

  9. 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

  10. 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.

  11. C60-mediated hydrogen desorption in Li-N-H systems

    NASA Astrophysics Data System (ADS)

    Qian, Zhao; Li, Sa; Pathak, Biswarup; Moysés Araújo, C.; Ahuja, Rajeev; Jena, Puru

    2012-12-01

    Hydrogen desorption from a LiH + NH3 mixture is very difficult due to the formation of the stable LiNH4 compound. Using cluster models and first-principles theory, we demonstrate that the C60 molecule can in fact significantly improve the thermodynamics of ammonia-mediated hydrogen desorption from LiH due to the stabilization of the intermediate state, LiNH4. The hydrogen desorption following the path of LiNH4-C60 → LiNH3-{{C}}_{6 0}+\\frac{1}{2}{{H}}_{2} is exothermic. Molecular dynamic simulations show that this reaction can take place even at room temperature (300 K). In contrast, the stable LiNH4 compound cannot desorb hydrogen at room temperature in the absence of C60. The introduction of C60 also helps to restrain the NH3 gas which is poisonous in proton exchange membrane fuel cell applications.

  12. C60-mediated hydrogen desorption in Li-N-H systems.

    PubMed

    Qian, Zhao; Li, Sa; Pathak, Biswarup; Araújo, C Moysés; Ahuja, Rajeev; Jena, Puru

    2012-12-01

    Hydrogen desorption from a LiH + NH(3) mixture is very difficult due to the formation of the stable LiNH(4) compound. Using cluster models and first-principles theory, we demonstrate that the C(60) molecule can in fact significantly improve the thermodynamics of ammonia-mediated hydrogen desorption from LiH due to the stabilization of the intermediate state, LiNH(4). The hydrogen desorption following the path of LiNH(4)-C(60) → LiNH(3)-C(60) + 1/2H(2) is exothermic. Molecular dynamic simulations show that this reaction can take place even at room temperature (300 K). In contrast, the stable LiNH(4) compound cannot desorb hydrogen at room temperature in the absence of C(60). The introduction of C(60) also helps to restrain the NH(3) gas which is poisonous in proton exchange membrane fuel cell applications. PMID:23138595

  13. 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

  14. Desorption of bis(2-chloroethyl) sulfide, mustard agent, from the surface of hardened cement paste (HCP) wafers.

    PubMed

    Tang, Hairong; Zhou, Xuezhi; Guan, Yingqiang; Zhou, Liming; Wang, Xinming; Yan, Huijuan

    2013-05-01

    The decontamination of surfaces exposed to chemical warfare agents is an interesting scientific topic. The desorption behavior of bis(2-chloroethyl) sulfide (sulfur mustard, HD) from the surface of the HD-contaminated hardened cement paste (HCP) was investigated under different weather conditions, which should provide scientific reference data for protection and decontamination projects involving HD-contaminated HCP in different conditions. The desorption of HD from the surface of HCP wafers was studied, and the effects of the purge air flow rate, water content, sorption temperature, and substrate age were investigated. HD desorption was detected from the surface of HD-contaminated HCP, but the desorption velocity was relatively slow. The desorption quantity remained within an order of magnitude throughout a time span of 36h (25°C at 200mL/min of purge air), and the amount of HD that was desorbed from each square meter of HCP surface was approximately 1.1g (25°C at 200mL/min of purge air), which was approximately 5.5 percent of the total HD that was initially applied. A higher flow rate of the purge air, increased water content, and longer substrate age of HCP all increased the HD desorption. In contrast, increased temperatures suppressed HD desorption. PMID:23395389

  15. 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.

  16. 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.

  17. 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 Rényi 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.

  18. BEAM PIPE DESORPTION RATE IN RHIC.

    SciTech Connect

    HUANG, H.; FISCHER, W.; HE, P.; HSEUH, H.C.; IRISO, U.; PTITSYN, V.; TRBOJEVIC, D.; WEI, J.; YANG, S.Y.

    2006-06-23

    In the past, an increase of beam intensity in RHIC has caused several decades of pressure rises in the warm sections during operation. This has been a major factor limiting the RHIC luminosity. About 430 meters of NEG coated beam pipes have been installed in the warm sections to ameliorate this problem. Beam ion induced desorption is one possible cause of pressure rises. A series beam studies in RHIC has been dedicated to estimate the desorption rate of various beam pipes (regular and NEG coated) at various warm sections. Correctors were used to generate local beam losses and consequently local pressure rises. The experimental results are presented and analyzed in this paper.

  19. Laser-induced desorption from sapphire surfaces

    SciTech Connect

    Hamza, A.V.; Schildbach, M.A.

    1992-03-01

    Laser-induced desorption of energetic ({approximately}7eV) aluminum ions was observed from clean and water-covered sapphire (1102) surfaces using time-of-flight mass spectrometry with laser wavelengths of 1064, 355, and 266 nm. In sharp contrast, O{sup +} (H{sup +} and OH{sup +}) ions were observed in electron-induced desorption measurements with 300 eV electrons from the bare (water- covered) (1102) surface. Sapphire surfaces were characterized with low energy electron diffraction, reflection electron energy loss spectroscopy, and Auger electron spectroscopy. 8 refs.

  20. Electronic Desorption of gas from metals

    SciTech Connect

    Molvik, A W; Kollmus, H; Mahner, E; Covo, M K; Bender, M; Bieniosek, F M; Kramer, A; Kwan, J; Prost, L; Seidl, P A; Westenskow, G

    2006-11-02

    During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. Direct aqueous injection with backflush thermal desorption for wastewater monitoring by online GC-MS.

    PubMed

    Ziemer, W; Wortberg, M; Eichberger, C; Gerstel, J; Kerl, W

    2010-06-01

    A gas chromatography-mass spectrometry system with a novel injector type, which is designed for direct aqueous injection of wastewater, is presented. The system is used for online monitoring of the influent of the wastewater treatment plant at BASF's main chemical production site in Ludwigshafen, Germany. The purpose of monitoring is to protect the biological treatment process and the receiving water body, the Rhine. The modular system is primarily based on commercial equipment, but utilizes a special injection system, which is connected to a Deans switch. The two-stage injector consists of a programmable temperature vaporizer (PTV) injector with a small volume insert for vaporization and a dual sorbent packed second PTV for analyte adsorption/desorption. The Deans switch allows a backflush/thermal desorption operation which enables the direct injection of filtered, crude wastewater. About 170 volatile and semivolatile compounds are calibrated with approximate detection limits of 1 mg/L, which are sufficient for the analysis of untreated wastewater. The quantitative results are transferred to a database which is connected to a process control system. If the wastewater does not meet the required specification, an alarm is generated and the wastewater is diverted into a storage basin. Special software programs and routines allow for reliable, unattended operation and remote instrument control. Data quality is automatically controlled in each run and through the daily analysis of quality control samples. The current design allows for analysis of volatile compounds, such as methanol, whereas an earlier injector setup restricted the range of analytes to less volatile compounds (of size C(4) or greater). PMID:20376433

  8. Adsorption and desorption of SO2, NO and chlorobenzene on activated carbon.

    PubMed

    Li, Yuran; Guo, Yangyang; Zhu, Tingyu; Ding, Song

    2016-05-01

    Activated carbon (AC) is very effective for multi-pollutant removal; however, the complicated components in flue gas can influence each other's adsorption. A series of adsorption experiments for multicomponents, including SO2, NO, chlorobenzene and H2O, on AC were performed in a fixed-bed reactor. For single-component adsorption, the adsorption amount for chlorobenzene was larger than for SO2 and NO on the AC. In the multi-component atmosphere, the adsorption amount decreased by 27.6% for chlorobenzene and decreased by 95.6% for NO, whereas it increased by a factor of two for SO2, demonstrating that a complex atmosphere is unfavorable for chlorobenzene adsorption and inhibits NO adsorption. In contrast, it is very beneficial for SO2 adsorption. The temperature-programmed desorption (TPD) results indicated that the binding strength between the gas adsorbates and the AC follows the order of SO2>chlorobenzene > NO. The adsorption amount is independent of the binding strength. The presence of H2O enhanced the component effects, while it weakened the binding force between the gas adsorbates and the AC. AC oxygen functional groups were analyzed using TPD and X-ray photoelectron spectroscopy (XPS) measurements. The results reveal the reason why the chlorobenzene adsorption is less affected by the presence of other components. Lactone groups partly transform into carbonyl and quinone groups after chlorobenzene desorption. The chlorobenzene adsorption increases the number of C=O groups, which explains the positive effect of chlorobenzene on SO2 adsorption and the strong NO adsorption. PMID:27155417

  9. 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.

  10. Cesium Sorption/Desorption Experiments with IONSIV(R) IE-911 in Radioactive Waste

    SciTech Connect

    Walker, D.D.

    2001-02-13

    This report describes cesium desorption from IONSIV IE-911 during ambient temperature storage and following temperature increases to 35 and 55 degrees C. This report also describes cesium sorption following return to ambient temperature. The IONSIV IE-911 used in these tests was loaded with cesium from Tank 44F radioactive waste in an ion exchange column test in 1999. Cesium desorbed and resorbed in the presence of Tank 44F waste and simulated waste solutions.

  11. Laser desorption mass spectrometry for molecular diagnosis

    NASA Astrophysics Data System (ADS)

    Chen, C. H. Winston; Taranenko, N. I.; Zhu, Y. F.; Allman, S. L.; Tang, K.; Matteson, K. J.; Chang, L. Y.; Chung, C. N.; Martin, Steve; Haff, Lawrence

    1996-04-01

    Laser desorption mass spectrometry has been used for molecular diagnosis of cystic fibrosis. Both 3-base deletion and single-base point mutation have been successfully detected by clinical samples. This new detection method can possibly speed up the diagnosis by one order of magnitude in the future. It may become a new biotechnology technique for population screening of genetic disease.

  12. 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...

  13. 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.

  14. 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.

  15. Desorption of Ag from Grain Boundaries in Ag Film on Br and H-Passivated Si(111) Surfaces

    SciTech Connect

    Roy, Anupam; Batabyal, R.; Mahato, J. C.; Dev, B. N.; Sundaravel, B.

    2011-07-15

    Growth of Ag film on Br- and H-passivated Si(111) surfaces was examined by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM) and photoemission electron microscopy (PEEM) techniques. The phenomenon of thermal grooving was observed after annealing at higher temperatures. Hierarchical desorption of Ag from the grain boundaries produce a fractal structure of Ag-depleted regions. Hierarchical desorption may be used for nanopatterning of the layer.

  16. 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.

  17. 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

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

    EPA Science Inventory

    This report details the Superfund Innovative Technology Evaluation of the Eco Logic International's gas-phase chemical reduction process, with an emphasis on their thermal desorption unit. he Eco Logic process employs a high temperature reactor filled with hydrogen as a means to ...

  19. 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...

  20. Dynamics of water desorption from a zeolite by a heated stream of inert gas

    SciTech Connect

    Bogoslovskaya, N.S.; Ustinova, E.A.; Seballo, A.A.

    1988-05-20

    Drying of gases, such as natural gas or air, by zeolites before low-temperature separation is now widely used in the national economy. A quart-glass adsorption-desorption apparatus was constructed for experimental study of gas drying and zeolite regeneration. The existence of a zone of water condensation was confirmed as the result of laboratory experiments conducted for study of thermal desorption of water from a zeolite by hot dry air, followed by calculations with the aid of a mathematical model of this process. Good agreement was found between the results of numerical calculations and laboratory experiments.

  1. 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

  2. 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.

  3. Desorption-assisted sun diver missions

    NASA Astrophysics Data System (ADS)

    Benford, Gregory; Benford, James

    2002-01-01

    Solar-driven sails which can also accelerate by ``boil off'' of coated materials offer new high-velocity missions. These can take advantage of high temperature characteristics of the sail by using the large solar flux at perihelion. For the near term use of beamed power, beam illumination at ~kW/cm2 in LEO can simulate conditions any solar grazer mission will experience to within 0.01 A.U. Sublimation (or desorption) thrust from LEO into interplanetary orbit can omit the several-year orbits conventional solar sails need to reach ~0.1 AU. A second ``burn'' at perihelion, the highest available orbital velocity in the inner solar system, and thus optimum point for a delta-V, then yields high velocities of ~50 km/s for >40 A.U. missions. The mission begins with deployment in Low Earth Orbit by conventional rocket. Then the launch begins, driven by a microwave beam (and much smaller solar photon thrust) from nearby in orbit. Beam heating makes a ``paint'' (polymer layer #1) desorp from the sail. Under this enhanced thrust, in repeated shots at perihelion in steepening elliptical orbits, the sail attains ~15 km/s velocity, canceling most of its solar orbital velocity, and so can fall edge-on toward the sun immediately. (This is far faster than using solar pressure to spiral down, which takes years.) It approaches the sun edge-on, to minimize radiation pressure on it in the inward fall. At perihelion the spacecraft rotates to face the sun. Under intense sunlight ~20 times Earth insolation, the sail desorps away polymer #2, getting a ~50 km/s boost at its maximum (infall) velocity. It then sails away as a conventional, reflecting solar sail, with the final Aluminum layer revealed. Its final speed is after leaving the solar potential well is ~10 AU/year. Within ~5 years, it sails beyond Pluto, giving high velocity mapping of the outer solar system, the heliopause and interstellar medium. .

  4. 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.

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

    PubMed

    Godin, Jean-Philippe; Hopfgartner, Gérard; 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Purex canyon exhaust fan bearing temperature monitoring system doric 245 datalogger programming

    SciTech Connect

    Blackaby, W.B.

    1994-09-06

    A micro-processor based datalogger is used to monitor, display, and log seventeen RTD temperature channels. Five bearings are monitored for each of the three electric motor-fan assemblies and two bearings are monitored on the steam turbine unit. Several alarms per data channel (a High alarm at 236 degrees and a High High alarm at 246 degrees F) will alert the operation`s staff to increasing abnormal bearing temperatures. This procedure is cross-referenced to the manufacturers manual. All programming steps will have the following footnote: Mpg x-xx. The Mpg refers to the Manual page, with x as the section number and xx as the page number in that section. When more information is needed, such as pictures or details, then the manual section and page number is provided.

  14. 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.

  15. 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.

  16. Catalytic oxidation of propylene--7. Use of temperature programmed reoxidation to characterize. gamma. -bismuth molybdate

    SciTech Connect

    Uda, T.; Lin, T.T.; Keulks, G.W.

    1980-03-01

    Temperature-programed reoxidation of propylene-reduced ..gamma..-Bi/sub 2/MoO/sub 6/ revealed a low-temperature peak (LTP) at 158/sup 0/C and a high-temperature peak (HTP) at 340/sup 0/C. Auger spectroscopy and X-ray diffraction of reduced and partially or completely reoxidized bismuth molybdate showed that at the LTP, molybdenum(IV) is oxidized to molybdenum(VI) and bismuth, from the metallic state to an oxidation state between zero and three, and that the HTP is associated with the complete oxidation of bismuth to bismuth(III). Activity tests for propylene oxidation showed lower acrolein formation on the catalyst, on which only the LTP was reoxidized than on catalysts on which both peaks were reoxidized. The reoxidation kinetics of the catalyst under conditions corresponding to the LTP showed an activation energy of 22.9 kcal/mole below 170/sup 0/C and near zero above 170/sup 0/C; the break in the Arrhenius plot of reoxidation of the catalyst under conditions corresponding to the HTP was at 400/sup 0/C, with activation energies of 46 kcal/mole at lower and near zero at higher temperatures. Propylene oxidation was apparently rate-limited by the HTP reoxidation process below 400/sup 0/C and by allylic hydrogen abstraction above 400/sup 0/C.

  17. 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.

  18. A basic program for calculating subsurface water temperatures using chemical geothermometers-implication to geothermal reservoir estimation

    NASA Astrophysics Data System (ADS)

    El-Naqa, Ali; Zeid, Nasser Abu

    1993-11-01

    GEOTHERM is a computer program written in BASIC language to estimate geothermal reservoir temperature using the well-known chemical gèothermometers. The empirical equations used in the program were obtained from the literature. Three different chemical geothermometers are included in the program: Na-K, Na-K-Ca, and silica geothermometers; this gives the user the opportunity not only to select the most reliable geothermometer in estimating subsurface temperature, but also to select the type of geothermometer according to available data. A sample input file of geothermal waters obtained from Iceland has been tested, so as to show the applicability and usefulness of the program.

  19. Effects of breeder feeding restriction programs and incubation temperatures on progeny footpad development.

    PubMed

    Da Costa, M J; Oviedo-Rondón, E O; Wineland, M J; Wilson, J; Montiel, E

    2014-08-01

    Footpad dermatitis begins early in life, and there is evidence of individual susceptibility. An experiment was conducted to evaluate the carryover effects of breeder feed restriction programs and incubation temperatures (TEM) on progeny footpad development at hatch, and 7 and 22 d. Cobb 500 fast feathering breeders were subjected to 2 dietary feed restriction programs during rearing: skip-a-day (SAD) and every-day feeding (EDF). At 60 wk of age, eggs from each group were collected and incubated according to 2 TEM, standard (S) eggshell temperature (38.1°C) and early-low late-high (LH). This second profile had low (36.9°C) eggshell temperature for the first 3 d, and standard temperature until the last 3 d when eggs were subjected to elevated (38.9°C) eggshell temperature. At hatch, 15 chicks from each treatment combination were sampled to obtain footpads for histological analysis. Seventy-two chicks per treatment were placed in 48 cages (6/cage), and raised to 22 d. At 7 and 22 d, 1 and 2 chickens, respectively, were sampled for footpads. The BW and group feed intake were recorded to obtain BW gain and feed conversion ratio at 7 and 21 d. Histological analysis assessed thickness and total area of stratus corneum (SC), epidermis, and dermis, and total papillae height. Data were analyzed as randomized complete block design in a 2 × 2 factorial arrangement of treatments. There was a negative effect of LH TEM on performance at both ages. An interaction effect on SC area and papillae height was observed at hatch. Additionally, SAD treatment increased thickness and area of footpad dermis. At 7 d, the SC parameters of the SAD progeny were increased. Epidermis thickness was affected by treatment interaction. Furthermore, LH TEM decreased epidermis thickness and dermis area. At 22 d, interaction effects were observed in thickness and area of SC and epidermis. Incubation S TEM increased thickness and area of dermis. It was concluded that breeder feed restriction programs and incubation TEM profiles may have carryover effects on histomorphological traits of footpads. PMID:24894526

  20. Sample Desorption/Onization From Mesoporous Silica

    DOEpatents

    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.

  1. 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.

  2. 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)

  3. 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

  4. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  6. Non-contact temperature measurement requirements of ground-based research and flight programs at JPL

    NASA Technical Reports Server (NTRS)

    Trinh, E. H.

    1989-01-01

    The Modular Containerless Processing Facility project is responsible for the development of flight equipment and of the accompanying scientific and technological research necessary to carry out containerless investigations in the low gravity of earth orbit. The requirement for sample temperature measurement is just one of the many physical properties determination needs that must be satisfied before the useful exploitation of low gravity and containerless experimentation techniques can be achieved. The specific implementation of temperature measurement for the ground-based research program is different from that of the flight hardware development project. The needs of the latter must also be differentiated according to the chronological order of the relevant space flight missions. Immediate demands of Spacelab instruments must be addressed by the adaptation of existing reliable technology to the special and restrictive on-orbit environment, while more advanced and yet unperfected techniques will be assigned to enterprises further in the future. The wide range of application of the containerless methods to the study of phenomena involving different states of matter and environmental conditions requires the satisfaction of a variety of boundary conditions through different approaches. An important issue to be resolved will be whether an integrated program dedicated to solve the problems of all the microgravity experimental effort will allow the solution of specific demands of existing as well as future flight equipment.

  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. 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 sol–gel 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 600°C. 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 μs 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 85°C) and 10% (at 125°C) 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-κ sol–gel film. PMID:23899050

  9. Shell/METC high-temperature, high-pressure filtration program

    SciTech Connect

    Salter, J.A.; Rockey, J.M.

    1995-12-31

    The purpose of this paper is to present the program objectives and non-proprietary results of the high temperature, high pressure filtration work done under the Shell/METC Cooperative Research and Development Agreement (CRADA) 93-011. The primary purpose of this CRADA was to collect data relevant to the design and operation of dry particulate solids filters employing rigid ceramic (silicon carbide) filter elements in a gasifying environment at conditions of commercial interest; e.g., temperatures up to 1100 {degrees}F and system pressures between 300 and 350 psia. Shell provided the ceramic filter elements and evaluated the exposed filter elements. METC installed the filter elements and operated their 10 inch Fluid Bed Gasification and Cleanup facility as required for their Hot Gas Clean-up Test Program. Filter elements were removed from service after approximately 254, 525 and 868 hours of on-line operation. The exposed filter elements were analyzed and compared to an unexposed element with respect to changes in physical property.

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

    NASA Astrophysics Data System (ADS)

    Chang, Yuan-Ming; Yang, Wen-Luh; Liu, Sheng-Hsien; Hsiao, Yu-Ping; Wu, Jia-Yo; Wu, Chi-Chang

    2013-07-01

    In this study, a high-performance Ti x Zr y Si z O flash memory is demonstrated using a sol-gel 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 600°C. 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 μs 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 85°C) and 10% (at 125°C) charge loss. The barrier height of the Ti x Zr y Si z O 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- κ sol-gel film.

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

    PubMed

    Chang, Yuan-Ming; Yang, Wen-Luh; Liu, Sheng-Hsien; Hsiao, Yu-Ping; Wu, Jia-Yo; Wu, Chi-Chang

    2013-01-01

    In this study, a high-performance TixZrySizO flash memory is demonstrated using a sol-gel 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 600°C. 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 μs 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 85°C) and 10% (at 125°C) 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-κ sol-gel film. PMID:23899050

  12. 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

  13. 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

  14. Comprehensive two-dimensional gas chromatographic separations with a temperature programmed microfabricated thermal modulator.

    PubMed

    Collin, William R; Nuñovero, Nicolas; Paul, Dibyadeep; Kurabayashi, Katsuo; Zellers, Edward T

    2016-04-29

    Comprehensive two-dimensional gas chromatography (GC×GC) with a temperature-programmed microfabricated thermal modulator (μTM) is demonstrated. The 0.78cm(2), 2-stage μTM chip with integrated heaters and a PDMS coated microchannel was placed in thermal contact with a solid-state thermoelectric cooler and mounted on top of a bench scale GC. It was fluidically coupled through heated interconnects to an upstream first-dimension ((1)D) PDMS-coated capillary column and a downstream uncoated capillary or second-dimension ((2)D) PEG-coated capillary. A mixture of n-alkanes C6-C10 was separated isothermally and the full-width-at-half-maximum (fwhm) values of the modulated peaks were assessed as a function of the computer-controlled minimum and maximum stage temperatures of μTM, Tmin and Tmax, respectively. With Tmin and Tmax fixed at -25 and 100°C, respectively, modulated peaks of C6 and C7 had fwhm values<53ms while the modulated peaks of C10 had a fwhm value of 1.3s, due to inefficient re-mobilization. With Tmin and Tmax fixed at 0 and 210°C, respectively, the fwhm value for the modulated C10 peaks decreased to 67ms, but C6 and C7 exhibited massive breakthrough. By programming Tmin from -25 to 0°C and Tmax from 100 to 220°C, the C6 and C7 peaks had fwhm values≤50ms, and the fwhm for C10 peaks remained<95ms. Using the latter conditions for the GC×GC separation of a sample of unleaded gasoline yielded resolution similar to that reported with a commercial thermal modulator. Replacing the PDMS phase in the μTM with a trigonal-tricationic room temperature ionic liquid eliminated the bleed observed with the PDMS, but also reduced the capacity for several test compounds. Regardless, the demonstrated capability to independently temperature program this low resource μTM enhances its versatility and its promise for use in bench-scale GC×GC systems. PMID:27036209

  15. 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

  16. Role of microstructure and heat treatments on the desorption kinetics of tritium from austenitic stainless steels

    NASA Astrophysics Data System (ADS)

    Chêne, J.; Brass, A.-M.; Trabuc, P.; Gastaldi, O.

    2007-02-01

    The liquid scintillation counting of solid samples (LSC-SS technique) was successfully used to study the role of microstructure and heat treatments on the behavior of residual tritium in several austenitic stainless steels (as-cast remelted tritiated waste, 316LN and 321 steels). The role of desorption annealing in the 100-600 °C range on the residual amount of tritium in tritiated waste was investigated. The residual tritium concentration computed from surface activity measurements is in good agreement with experimental values measured by liquid scintillation counting after full dissolution of the samples. The kinetics of tritium desorption recorded with the LSC-SS technique shows a significant desorption of residual tritium at room temperature, a strong barrier effect of thermal oxide films on the tritium desorption and a dependance of the tritium release on the steels microstructure. Annealing in the 300-600 °C range allows to desorb a large fraction of the residual tritium. However a significant trapping of tritium is evidenced. The influence of trapping phenomena on the concentration of residual tritium and on its dependance with the annealing temperature was investigated with different recrystallized and sensitized microstructures. Trapping is evidenced mainly below 150 °C and concerns a small fraction of the total amount of tritium introduced in austenitic steels. It presumably occurs preferentially on precipitates such as Ti(CN) or on intermetallic phases.

  17. 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.

  18. 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

  19. Electron stimulated desorption of H 3O + from 316L stainless steel

    NASA Astrophysics Data System (ADS)

    Cole, C. R.; Outlaw, R. A.; Champion, R. L.; Holloway, B. C.; Kelly, M. A.

    2007-02-01

    Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr 2O 3. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p 3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H 2) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H 3O + peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H 3O +, as well as its constituents (H +, O + and OH +) and a small amount of fluorine as F -, but no F + or F + complexes (HF +, etc.). An electron stimulated desorption cross-section of σ+ ˜ 1.4 × 10 -20 cm 2 was determined for H 3O + from 316L stainless steel for hydrogen residing in surface chromium hydroxide.

  20. 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

  1. Desorption Studies of DDGS under Varying CDS and Temperature Levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Distillers dried grains with solubles (DDGS) often contains approximately 30-35% (db) protein and 10-12% (db) fat, and has been shown to be an excellent livestock feed. DDGS is produced from the fuel ethanol industry, which is located in the midwest US; there is a growing need to transport DDGS over...

  2. 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.

  3. 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.

  4. Effects of H2O and H2O2 on Thermal Desorption of Tritium from Stainless Steel

    SciTech Connect

    Quinlan, M.J.; Shmayda, W.T.; Lim, S.; Salnikov, S.; Chambers, Z.; Pollock, E.; Schroder, W.U.

    2010-03-12

    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 H2O or H2O2 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.

  5. 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

  6. 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.

  7. Adsorption and desorption of chlorpyrifos to soils and sediments.

    PubMed

    Gebremariam, Seyoum Yami; Beutel, Marc W; Yonge, David R; Flury, Markus; Harsh, James B

    2012-01-01

    Chlorpyrifos, one of the most widely used insecticides, has been detected in air, rain, marine sediments, surface waters, drinking water wells, and solid and liquid dietary samples collected from urban and rural areas. Its metabolite, TCP, has also been widely detected in urinary samples collected from people of various age groups. With a goal of elucidating the factors that control the environmental contamination, impact, persistence, and ecotoxicity of chlorpyrifos, we examine, in this review, the peer-reviewed literature relating to chlorpyrifos adsorption and desorption behavior in various solid-phase matrices. Adsorption tends to reduce chlorpyrifos mobility, but adsorption to erodible particulates, dissolved organic matter, or mobile inorganic colloids enhances its mobility. Adsorption to suspended sediments and particulates constitutes a major off-site migration route for chlorpyrifos to surface waters, wherein it poses a potential danger to aquatic organisms. Adsorption increases the persistence of chlorpyrifos in the environment by reducing its avail- ability to a wide range of dissipative and degradative forces, whereas the effect of adsorption on its ecotoxicity is dependent upon the route of exposure. Chlorpyrifos adsorbs to soils, aquatic sediments, organic matter, and clay minerals to differing degrees. Its adsorption strongly correlates with organic carbon con- tent of the soils and sediments. A comprehensive review of studies that relied on the batch equilibrium technique yields mean and median Kd values for chlorpyrifos of 271 and 116 L/kg for soils, and 385 and 403 L/kg for aquatic sediments. Chlorpyrifos adsorption coefficients spanned two orders of magnitude in soils. Normalizing the partition coefficient to organic content failed to substantially reduce variability to commonly acceptable level of variation. Mean and median values for chlorpyrifos partition coefficients normalized to organic carbon, K, were 8,163 and 7,227 L/kg for soils and 13,439 and 15,500 L/kg for sediipents. This variation may result from several factors, including various experimental artifacts, variation in quality of soil organic matter, and inconsistencies in experimental methodologies. Based on this review, there appears to be no definitive quantification of chlorpyrifos adsorption or desorption characteristics. Thus, it is difficult to predict its adsorptive behavior with certainty, without resorting to experimental methods specific to the soil or sediment of interest. This limitation should be recognized in the context of current efforts to predict the risk, fate, and transport of chlorpyrifos based upon published partition coefficients. Based on a comprehensive review of the peer-reviewed literature related to adsorption and desorption of chlorpyrifos, we propose the following key areas for future research. From this review, it becomes increasingly evident that pesticide partitioning cannot be fully accounted for by the fraction of soil or solid-matrix organic matter or carbon content. Therefore, research that probes the variation in the nature and quality of soil organic matter on pesticide adsorption is highly desirable. Pesticide persistence and bioavailability depend on insights into desorption capacity. Therefore, understanding the fate and environmental impact of hydrophobic pesticides is incomplete without new research being performed to improve insights into pesticide desorption from soils and sediments. There is also a need for greater attention and consistency in developing experimental methods aimed at estimating partition coefficients. Moreover, in such testing, choosing initial concentrations and liquid-solid ratios that are more representative of environmental conditions could improve usefulness and interpretation of data that are obtained. Future monitoring efforts should include the sampling and analysis of suspended particulates to account for suspended solid-phase CPF, a commonly underestimated fraction in surface water quality monitoring programs. Finally, management practices related to the reduction of off-site migration of CPF should be further evaluated, including alternative agricultural practices leading to reduction in soil erosion and structural best management practices, such as sedimentation ponds, treatment wetlands, and vegetated edge-of-field strips. PMID:22057931

  8. 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

  9. 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...

  10. 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.

  11. 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, νn, of the Arrhenius equation. From the Arrhenius plot ln -θ/˙ θ 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.

  12. 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.

  13. Measurements and analysis of water adsorption and desorption

    SciTech Connect

    Monazam, E.R.; Shadle, L.J.; Schroeder, K.

    1996-02-01

    An investigation was carried out on the adsorption and desorption of moisture in chars of low rank coal. Equilibrium moisture sorptions of dry and moist chars were measured at room temperature and relative humidity of 30% and 80%. Based on these measurements, a novel mathematical model was developed to predict both the rate and the level of hydration for coals and chars. The formulation uses a shrinking core model which required only the measurement of the adsorbing material`s equilibrium moisture content at different temperatures and humidities. The model was validated against experimental and literature data. It accurately and reliably predicted both the rate and extent of hydration and dehydration for coals and char. Using this model, the effects of varying temperatures, relative humidities, and size of the particles and coal pile were simulated. The sensitivity study demonstrated that, as expected, relative humidity and temperature had strong effects on both the rate of hydration and-the equilibrium moisture of coal or char. The particle size dramatically influenced the rate of hydration, but had no affect on the equilibrium moisture content. This model can be used effectively to simulate the impact of moisture on drying, storage, and spontaneous combustion of coals and coal-derived chars.

  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. 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.

  16. Laboratory study of sticking and desorption of H2 and its significance in the chemical evolution of dense interstellar medium

    NASA Astrophysics Data System (ADS)

    Acharyya, K.

    2014-09-01

    The temperature-programmed desorption spectra of H2 is recorded under ultrahigh vacuum conditions on an olivine substrate with more than 90 per cent forsterite content for different coverage and temperatures. Then, using an empirical kinetic model, binding energy of H2 on the substrate is found to be 480 ± 10 K (41.36 ± 0.86 meV). Lower limit of sticking coefficient is estimated by comparing gas load at room temperature and at low temperature, which varies between 0.82 and 0.25 for temperatures between 7 and 14 K. Using a gas-grain chemical network, it is found out that a steady state is reached around after 50 yr at 10 K and both the steady-state abundance and time required to attend steady state is a strong function of temperature. Then, this model is used to check the effect of sticking of H2 on the grain surface chemistry. It is found that for H2O, CH4, NH3 and HCN, abundance due to reaction pathways involving H2 is within 1 per cent, when compared with the abundance achieved considering most dominant pathways. Thus, neglecting sticking of H2 will not change overall abundance of these molecules. For carbon chain molecules, it was found that the reaction pathways with H2 may be important and could contribute significantly to account for the observed abundances. Since, sticking of H2 is temperature sensitive, increase in temperature will reduce the effect of these reactions.

  17. 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.

  18. 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.

  19. 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

  20. 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, CaCl₂ and NaNO₃) 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 (ω ≈ 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

  1. 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.

  2. 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.

  3. Model for the catalytic oxidation of CO, including gas-phase impurities and CO desorption

    NASA Astrophysics Data System (ADS)

    Buendía, G. M.; Rikvold, P. A.

    2013-07-01

    We present results of kinetic Monte Carlo simulations of a modified Ziff-Gulari-Barshad model for the reaction CO+O → CO2 on a catalytic surface. Our model includes impurities in the gas phase, CO desorption, and a modification known to eliminate the unphysical O poisoned phase. The impurities can adsorb and desorb on the surface, but otherwise remain inert. In a previous work that did not include CO desorption [Buendía and Rikvold, Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.85.031143 85, 031143 (2012)], we found that the impurities have very distinctive effects on the phase diagram and greatly diminish the reactivity of the system. If the impurities do not desorb, once the system reaches a stationary state, the CO2 production disappears. When the impurities are allowed to desorb, there are regions where the CO2 reaction window reappears, although greatly reduced. Following experimental evidence that indicates that temperature effects are crucial in many catalytic processes, here we further analyze these effects by including a CO desorption rate. We find that the CO desorption has the effect to smooth the transition between the reactive and the CO rich phase, and most importantly it can counteract the negative effects of the presence of impurities by widening the reactive window such that now the system remains catalytically active in the whole range of CO pressures.

  4. Effect of programmed diurnal temperature cycles on plasma thyroxine level, body temperature, and feed intake of holstein dairy cows

    NASA Astrophysics Data System (ADS)

    Scott, I. M.; Johnson, H. D.; Hahn, G. L.

    1983-03-01

    Holstein cows exposed to simulated summer diurnal ambient temperature cycles of Phoenix, Arizona and Atlanta, Georgia and diurnal modifications of these climates displayed daily cycles fluctuations in plasma thyroxine (T4) and rectal temperatures (Tre). There were daily diurnal changes in T4 and Tre under all simulated climate conditions. Maximal values generally occurred in the evening hours and minimum values in the morning. Although the diurnal rhythm was influenced by the various simulated climates (diurnal modifications) a diurnal rhythm was very evident even under constant conditions at thermoneutral (Tnc) and at cyclic thermoneutral conditions (TN). The major significance of the study is that the initiation of night cooling of the animals at a time when their Tre was highest was most beneficial to maintenance of a TN plasma T4 level. There was a highly significant negative relationship of average T4 and average Tre. There was also a significant negative relationship of feed consumption and average temperature-humidity index (THI). These data suggest that night cooling may be a most effective method to alleviate thermoregulatory limitations of a hot climate on optimal animal performance. Decreasing the night time air temperature (Ta) or THI or increasing the diurnal range allows the cows to more easily dissipate excess body heat accumulated during the day and minimize the thermal inhibition on feed intake, and alterations in plasma T4 and Tre.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Salt tolerance of desorption electrospray ionization (DESI).

    PubMed

    Jackson, Ayanna U; Talaty, Nari; Cooks, R Graham; Van Berkel, Gary J

    2007-12-01

    The salt tolerance of desorption electrospray ionization (DESI) was systematically investigated by examining three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl (1:1) from different surfaces. At physiological salt concentrations, the individual drugs in each mixture were observed in each experiment. Even at salt concentrations significantly above physiological levels, particular surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest in low nanogram amounts. Salt adducts, which are observed even in the absence of added salt, could be eliminated by adding 0.1% 7 M 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 better signal/noise characteristics for DESI. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution. PMID:17977744

  11. Coincidence experiments in desorption mass spectrometry

    NASA Astrophysics Data System (ADS)

    Diehnelt, C. W.; English, R. D.; Van Stipdonk, M. J.; Schweikert, E. A.

    2002-06-01

    The detection of coincidental signals can enhance the amount of information available in desorption time-of-flight mass spectrometry (TOF-MS) by identifying physical, chemical and/or spatial correlations between secondary ions. Detection of coincidental emissions requires that the target surface be bombarded with individual primary ions (keV or MeV), each resolved in time and space. This paper will discuss the application of coincidence counting to TOF-MS to: extract the secondary ion mass spectrum and secondary ion yields from an organic target produced by a single primary ion type when multiple primary ions simultaneously impact the sample; examine the metastable dissociation pathways and decay fractions of organic secondary ions using an ion-neutral correlation method; and study the chemical microhomogeneity (on the sub-μm scale) of a surface composed of two chemically distinct species.

  12. 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.

  13. Soil temperature modeling at different depths using neuro-fuzzy, neural network, and genetic programming techniques

    NASA Astrophysics Data System (ADS)

    Kisi, Ozgur; Sanikhani, Hadi; Cobaner, Murat

    2016-05-01

    The applicability of artificial neural networks (ANN), adaptive neuro-fuzzy inference system (ANFIS), and genetic programming (GP) techniques in estimating soil temperatures (ST) at different depths is investigated in this study. Weather data from two stations, Mersin and Adana, Turkey, were used as inputs to the applied models in order to model monthly STs. The first part of the study focused on comparison of ANN, ANFIS, and GP models in modeling ST of two stations at the depths of 10, 50, and 100 cm. GP was found to perform better than the ANN and ANFIS-SC in estimating monthly ST. The effect of periodicity (month of the year) on models' accuracy was also investigated. Including periodicity component in models' inputs considerably increased their accuracies. The root mean square error (RMSE) of ANN models was respectively decreased by 34 and 27 % for the depths of 10 and 100 cm adding the periodicity input. In the second part of the study, the accuracies of the ANN, ANFIS, and GP models were compared in estimating ST of Mersin Station using the climatic data of Adana Station. The ANN models generally performed better than the ANFIS-SC and GP in modeling ST of Mersin Station without local climatic inputs.

  14. 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.

  15. Copper desorption from Gelidium algal biomass.

    PubMed

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

    2007-04-01

    Desorption of divalent copper from marine algae Gelidium sesquipedale, an algal waste (from agar extraction industry) and a composite material (the algal waste immobilized in polyacrylonitrile) was studied in a batch system. Copper ions were first adsorbed until saturation and then desorbed by HNO(3) and Na(2)EDTA solutions. Elution efficiency using HNO(3) increases as pH decreases. At pH=1, for a solid to liquid ratio S/L=4gl(-1), elution efficiency was 97%, 95% and 88%, the stoichiometric coefficient for the ionic exchange, 0.70+/-0.02, 0.73+/-0.05 and 0.76+/-0.06 and the selectivity coefficient, 0.93+/-0.07, 1.0+/-0.3 and 1.1+/-0.3, respectively, for algae Gelidium, algal waste and composite material. Complexation of copper ions by EDTA occurs in a molar proportion of 1:1 and the elution efficiency increases with EDTA concentration. For concentrations of 1.4, 0.88 and 0.57 mmoll(-1), the elution efficiency for S/L=4gl(-1), was 91%, 86% and 78%, respectively, for algae Gelidium, algal waste and composite material. The S/L ratio, in the range 1-20gl(-1), has little influence on copper recovery by using 0.1M HNO(3). Desorption kinetics was very fast for all biosorbents. Kinetic data using HNO(3) as eluant were well described by the mass transfer model, considering the average metal concentration in the solid phase and the equilibrium relationship given by the mass action law. The homogeneous diffusion coefficient varied between 1.0 x 10(-7)cm(2)s(-1) for algae Gelidium and 3.0 x 10(-7)cm(2)s(-1) for the composite material. PMID:17276480

  16. 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.

  17. 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.

  18. Analysis of Desorbed Gases from Surface: Thermal Desorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Inayoshi, Sakae S.

    Thermal desorption spectroscopy (TDS) has been commonly employed to evaluate the outgassing properties of both vacuum materials and thin films. Hydrogen, water, CO and CO2 —the most dominant gas species— can be easily detected and quantified by quadrupole mass spectrometry. This paper examines two calibration methods to convert ion current into outgassing rate: first, by using the standard leak of each gas and, second, by using an absolute pressure gauge. TDS is demonstrated for two different types of samples: stainless steel and amorphous Si (a-Si) film. In the case of stainless steel, samples blasted with glass beads were compared with chemically polished samples, and the TDS results' relationship to pumping down properties was investigated. The a-Si film examined was formed using a low temperature poly silicon process. Its hydrogen concentration as determined by TDS corresponded with that obtained by secondary ion mass spectrometry (SIMS). The outgassing temperature characteristics obtained for both the stainless steel and a-Si samples provided valuable information.

  19. Kinetics of low-temperature CO oxidation on Au(111)

    NASA Astrophysics Data System (ADS)

    Thuening, Theodore; Walker, Joshua; Adams, Heather; Furlong, Octavio; Tysoe, Wilfred T.

    2016-06-01

    The oxidation of carbon monoxide on oxygen-modified Au(111) surfaces is studied using a combination of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). TPD reveals that CO desorbs in two states with the low-temperature state have a peak temperature between ~ 130 and 150 K, and the higher-temperature state having a peak temperature that varies from ~ 175 to ~ 220 K depending on the initial oxygen and CO coverages. Infrared spectroscopy indicates that the low-temperature CO desorption state is predominantly associated with CO adsorbed on Auδ + sites, while the higher-temperature states are due to CO on Au0 sites. No additional vibrational features are detected indicating that CO reacts directly with adsorbed atomic oxygen on gold to form CO2. Estimates of the activation energy for CO2 formation suggest that they are in the same range and found for supported gold catalysts at reaction temperature below ~ 300 K.

  20. 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%.

  1. 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.

  2. Characterization of trace metal desorption using electrothermal atomic absorption spectroscopy

    SciTech Connect

    Fonseca, R.W.

    1993-01-01

    The desorption characteristics of several metals have been studied using electrothermal atomic absorption spectroscopy (ETAAS). Activation energies and orders of release obtained from the atomic absorption profiles provided the main tools to draw conclusions about the different systems. Different factors affecting the absorption profiles were studied. Vaporization was carried out from different substrates including graphite, Ta and alumina. Different heating rates, drying temperatures and thermal pretreatment temperatures were studied. Chemisorption of gases onto the graphite prior to the sample deposition and roughening of the substrates surface using abrasives were also evaluated. ETAAS data provides information concerning the degree of metal-substrate interaction which is elemental dependent. Changes in activation energies as a result of variations in the thermal treatment of the sample revealed changes in the distribution of the analyte on the surface. The metal geometry and its distribution on the surface was also affected by changes in the substrate. Metals such as Ag and Au seemed to move on the surface and disperse to smaller particles when the temperature of the substrate reached the Tammann temperature for the respective metal. Given the potential of ETAAS to provide surface information a tube-in-tube atomizer was designed to make the technique more amenable for this type of investigation. Metal migration into different types of graphite was studied. Metals appeared to migrate several microns through imperfections on the substrate surface. The main effect of this migration on the atomic absorption profiles seemed to be an increase in tailing of the back edge. Finally, several methods used to evaluate kinetic parameters from ETAAS data were compared. One of the methods does not seem to discriminate order of release different than unity. However, the others did yield reasonable results for the metals studied with good correlations among them.

  3. Technical Note: In-situ derivatization thermal desorption GC-TOFMS for direct analysis of particle-bound non-polar and polar organic species

    NASA Astrophysics Data System (ADS)

    Orasche, J.; Schnelle-Kreis, J.; Abbaszade, G.; Zimmermann, R.

    2011-05-01

    An in-situ derivatization thermal desorption method followed by gas chromatography and time-of-flight mass spectrometry (IDTD-GC-TOFMS) was developed for determination of polar organic compounds. Hydroxyl and carboxyl groups of compounds such as anhydrous sugars, alcohols and phenols, fatty acids and resin acids are targets of the derivatization procedure. Derivatization is based on silylation with N-Methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) during the step of thermal desorption. The high temperature of 300 °C during desorption is utilized for the in-situ derivatization on the collection substrate (quartz fibre filters) accelerating the reaction rate. Thereby, the analysis time is as short as without derivatization. At first the filter surface is dampened with derivatization reagent before insertion of the sample into the thermal desorption unit. To ensure ongoing derivatization during thermal desorption the carrier gas is saturated with MSTFA until the desorption procedure is finished. The method introduced here was compared with direct thermal desorption gas chromatography time-of-flight-mass spectrometry (DTD-GC-TOFMS) and with solvent extraction (SE) procedures followed by gas chromatography and mass spectrometry. Comparisons were carried out with field samples originating from ambient aerosol collected on quartz fibre filters. Moreover, the methods have been applied on NIST Standard Reference Material Urban Dust (SRM 1649a).

  4. 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.

  5. 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.

  6. 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.

  7. A possible answer to the mysterious non detection of hydroxylamine in space: the thermal desorption mechanism

    NASA Astrophysics Data System (ADS)

    Jonusas, Mindaugas; Krim, Lahouari

    2016-04-01

    The presence of NH2OH, one of the main precursors in the formation of amino-acids, on dust grain mantles, may be the most obvious elucidation for the creation of large prebiotic molecules in the interstellar medium. However, while many laboratory experimental studies, to simulate the icy grain chemistry in space, found that NH2OH molecules may be easily formed in solid phase with high abundances and then they should desorb, through a temperature induced desorption into the gas phase, with the same high abundances; all the spatial observations conclude that NH2OH is not detected in gas phase within any of the explored astronomical sources. Such inconsistencies between laboratory experiment simulations and spatial observations lead our investigations towards this experimental study to see if there is any chemical transformation of NH2OH, occurring in the solid phase before the desorption processes of NH2OH from the mantle of interstellar icy grains. Our experimental results show that the heating of NH2OH-H2O ices lead to a decomposition of NH2OH into HNO, NH3 and O2, even before reaching its desorption temperature. We show through this work that the NH2OH non-detection from previous examined astronomical sources could mainly due to its high reactivity in solid phase on the icy interstellar grains.

  8. 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 55°C and 135°C. 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

  9. 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.

  10. 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.

  11. 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.

  12. Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    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.

  13. 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

  14. 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.

  15. 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.

  16. [Desorption characteristics of phosphorus in tea tree rhizosphere soil].

    PubMed

    Yang, Wei; Zhou, Wei-Jun; Bao, Chun-Hong; Miao, Xiao-Lin; Hu, Wen-Min

    2013-07-01

    In order to explore the phosphorus (P) release process and its supply mechanism in tea tree rhizosphere soil, an exogenous P adsorption and culture experiment was conducted to study the P desorption process and characters in the tea tree rhizosphere soils having been cultivated for different years and derived from different parent materials. The least squares method was used to fit the isotherms of P desorption kinetics. There was an obvious difference in the P desorption process between the rhizosphere soils and non-rhizosphere soils. The P desorption ability of the rhizosphere soils was significantly higher than that of the non-rhizosphere soils. As compared with non-rhizosphere soils, rhizosphere soils had higher available P content, P desorption rate, and beta value (desorbed P of per unit adsorbed P), with the average increment being 5.49 mg x kg(-1), 1.7%, and 24.4%, respectively. The P desorption ability of the rhizosphere soils derived from different parent materials was in the order of granite > quaternary red clay > slate. The average available P content and P desorption ability of the rhizosphere soils increased with increasing cultivation years. PMID:24175512

  17. 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

  18. 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.

  19. Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

    NASA Astrophysics Data System (ADS)

    Paxton, W. F.; Brooks, M. M.; Howell, M.; Tolk, N.; Kang, W. P.; Davidson, J. L.

    2014-06-01

    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 × 1012 s-1 were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.

  20. 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.

  1. In Situ Atomic Force Microscopy Observation of the Desorption Process from Monomolecular Organic Layers of a Naphthalene Derivative

    NASA Astrophysics Data System (ADS)

    Miyamoto, Yusuke; Nemoto, Takashi; Yoshida, Kaname; Kurata, Hiroki; Isoda, Seiji

    2004-07-01

    A monomolecular crystalline layer of “1,4,5,8-naphthalene-tetracarboxylic-dianhydride” (NTCDA) on a highly oriented pyrolytic graphite (HOPG) substrate was formed by vacuum deposition. By estimating molecular packing in a crystal by scanning tunneling microscopy, a new structure of the monolayer was suggested, which is different from those reported previously. Molecules were observed to be standing perpendicular to the HOPG surface and packed in a face-to-face manner. A thermal desorption process was observed in the monomolecular layer by temperature-variable atomic force microscopy (AFM). The in situ AFM observation clarified that NTCDA molecules desorbed from the edges of crystals just above room temperature. Morphological changes at a constant temperature of 308 K were observed in detail, where desorption rates were concluded to be anisotropically dependent on crystalline edges. This dependency originated from the anisotropy of intermolecular interaction. The rate order of the desorption process, a kinetic parameter, was evaluated to be 0.2, which corresponds well to the desorption behavior observed by AFM.

  2. 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.

  3. 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

  4. 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.

  5. Microchannel membrane separation applied to confined thin film desorption

    SciTech Connect

    Thorud, Jonathan D.; Liburdy, James A.; Pence, Deborah V.

    2006-08-15

    The concept of a confined thin film to enhance the desorption process is based on a reduced mass diffusion resistance. A wide thin film is formed into a microchannel by using a porous membrane as one wall of the channel enabling vapor extraction along the flow. Heat added to the channel results in vapor generation and subsequent extraction through the membrane. This experimental study investigates the performance of vapor extraction as a function of confined thin film thickness, pressure difference across the membrane and inlet concentration to the microchannel. In addition, heat added to the system was varied and results are presented in terms of the wall superheat temperature relative to the inlet saturated conditions of the binary fluid. The test section was equipped with a transparent window to observe bubble formation and vapor extraction. Results show that the performance, measured by the vapor release rate, increases for reduced channel thickness, for increased pressure difference across the membrane, and for lower inlet concentration. Results show that lower wall superheat correspond to higher heat transfer coefficients. Trends of Nusselt number and Sherwood number versus both channel Reynolds number and the product of the Reynolds number and Schmidt number are presented. Bubble formation in the channel does not degrade overall performance provided a critical heat flux condition does not occur. (author)

  6. 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

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

    USGS Publications Warehouse

    Barker, Charles E.; Dallegge, Todd A.

    2005-01-01

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

  8. 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.

  9. 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.

  10. Laser-induced desorption of dimethylcadmium from silicon

    NASA Astrophysics Data System (ADS)

    Varakin, Vladimir N.; Panesh, Anatoly M.; Simonov, Alexander P.

    1990-07-01

    A method of laser-induced desorption mass spectrometry (LIDMS) has been used to examine the dynamics of Cd(CH3)2 chemisorption and spontaneous decomposition on n type Si(100) with native surface oxide, the pathways and efficiencies of the adsorbate desorption due to the absorption of the XeCl. laser radiation by silicon. The extremely fast processes in the adlayer re caused by the preceding irradiation of the surface of the sample by intensive (with fluences up to 0.4 J/cm2 ) laser pulses . The conet It ion between intact, dissociative, and recombination desorption pathways s responsible for the observed laser fluence dependences of the desorption of Cd(CH3)2 and its fragments.

  11. 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.

  12. 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.

  13. Carbohydrate and steroid analysis by desorption electrospray ionization mass spectrometry.

    PubMed

    Kauppila, Tiina J; Talaty, Nari; Jackson, Ayanna U; Kotiaho, Tapio; Kostiainen, Risto; Cooks, R Graham

    2008-06-21

    Desorption electrospray ionization mass spectrometry (DESI-MS) is applied to the analysis of carbohydrates and steroids; the detection limits are significantly improved by the addition of low concentrations of salts to the spray solvent. PMID:18535704

  14. 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 ...

  15. 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 ...

  16. Kinetics of alkanethiol monolayer desorption from gold in air.

    PubMed

    Shadnam, Mohammad Reza; Amirfazli, A

    2005-10-14

    Thermal desorption of an alkanethiol monolayer from a gold substrate into a gaseous medium under ambient pressure was investigated using XPS and it was found that there exist 2 consecutive 1st order kinetics mechanisms with activation energies of 29.9 and 32.7 kcal mol(-1), respectively, i.e. on average approximately 15% higher than reports for liquid media desorption. PMID:16193142

  17. 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.

  18. 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.

  19. Adsorption and desorption processes of MCPA in Polish mineral soils.

    PubMed

    Paszko, Tadeusz

    2011-01-01

    Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils. PMID:21722084

  20. Small molecules as substrates for adsorption/desorption in (252)CF plasma desorption mass spectrometry.

    PubMed

    Wolf, B; Macfarlane, R D

    1991-01-01

    Department of Chemistry, Texas A & M University, College Station, Texas, USA We present a new approach to substrate selection for californium-252 plasma desorption mass spectrometry ((252)Cf_PDMS) in which small volatile molecules that are water insoluble are used as matrices in place of the polymeric substrates used in previous studies. The desirable features of analyte adsorption are combined with the concept of using a volatile matrix to reduce the level of internal excitation of a desorbed analyte and to assist in ionization during the desorption process. Derivatives of anthracene were found to meet these requirements and to perform satisfactorily as substrates in (252)Cf-PDMS. Spectra were obtained for bovine insulin (m I z 5734) adsorbed onto 9-anthroic acid and 2-aminoanthracene and compared with spectra using a nitrocellulose substrate. Sharper peaks and lower backgrounds are observed when the 9-anthroic acid matrix is used, indicating reduced levels of internal excitation and initial kinetic energy for the desorbed molecular ion of insulin. A comparison of the performance of 9-anthroic acid and 2-aminoanthracene shows the influence of substrate functional groups on desorbed protein yields. Finally, the versatility of the small-molecule matrix concept is discussed with respect to selection of a range of functionality, solubility, and hydrophilicity. PMID:24242086

  1. 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.

  2. Adsorption and desorption of dissolved organic matter by carbon nanotubes: Effects of solution chemistry.

    PubMed

    Engel, Maya; Chefetz, Benny

    2016-06-01

    Increasing use of carbon nanotubes (CNTs) has led to their introduction into the environment where they can interact with dissolved organic matter (DOM). This study focuses on solution chemistry effects on DOM adsorption/desorption processes by single-walled CNTs (SWCNTs). Our data show that DOM adsorption is controlled by the attachment of DOM molecules to the SWCNTs, and that the initial adsorption rate is dependent on solution parameters. Adsorbed amount of DOM at high ionic strength was limited, possibly due to alterations in SWCNT bundling. Desorption of DOM performed at low pH resulted in additional DOM adsorption, whereas at high pH, adsorbed DOM amount decreased. The extent of desorption conducted at increased ionic strength was dependent on pre-adsorbed DOM concentration: low DOM loading stimulated additional adsorption of DOM, whereas high DOM loading facilitated release of adsorbed DOM. Elevated ionic strength and increased adsorbed amount of DOM reduced the oxidation temperature of the SWCNTs, suggesting that changes in the assembly of the SWCNTs had occurred. Moreover, DOM-coated SWCNTs at increased ionic strength provided fewer sites for atrazine adsorption. This study enhances our understanding of DOM-SWCNT interactions in aqueous systems influenced by rapid changes in salinity, and facilitates potential use of SWCNTs in water-purification technologies. PMID:26878603

  3. Sorption / desorption hysteresis of non-polar organic compounds in carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Wang, G.; Kleineidam, S.; Grathwohl, P.

    2003-04-01

    Natural and thermally-altered carbonaceous materials (coals, charcoal, cokes) are nowadays found in many soil and sediment samples due to anthropogenic impact (e.g. industrial activities, traffic) to the natural environment. The sorption -- desorption characteristics of hydrophobic organic compounds on that type of geosorbents play an important role in contaminant fate and transport and are yet not precisely known. Contaminant transport and bioavailibility models often assume complete sorption reversibility. In this study, a series of desorption steps using the ASE (accelerated solvent extractor) with water at different temperatures were carried out to determine the desorption enthalpy and to study hysteresis phenomena. The initial natural loading of PAHs onto the geosorbents was determined by solvent extraction (acetone and toluene). The background loading is in the order of 0.8 mg kg-1 -- 102 mg kg-1 for the natural coals and in the order of 0.16 mg kg-1 -- 10 mg kg-1 for the thermally altered coals. The results are compared to kinetic and equilibrium data from laboratory experiments on sorptive uptake of the phenanthrene onto the same carbonaceous samples.

  4. Evidence for a CO Desorption Front in the Outer AS 209 Disk

    NASA Astrophysics Data System (ADS)

    Huang, Jane; Öberg, Karin I.; Andrews, Sean M.

    2016-05-01

    Millimeter observations of CO isotopologues are often used to make inferences about protoplanetary disk gas density and temperature structures. The accuracy of these estimates depends on our understanding of CO freezeout and desorption from dust grains. Most models of these processes indicate that CO column density decreases monotonically with distance from the central star due to a decrease in gas density and freezeout beyond the CO snowline. We present ALMA Cycle 2 observations of 12CO, 13CO, and C18O J=2-1 emission that instead suggest CO enhancement in the outer disk of T Tauri star AS 209. Most notably, the C18O emission consists of a central peak and a ring at a radius of ∼ 1\\prime \\prime (120 au), well outside the expected CO snowline. We propose that the ring arises from the onset of CO desorption near the edge of the millimeter dust disk. CO desorption exterior to a CO snowline may occur via non-thermal processes involving cosmic rays or high-energy photons, or via a radial thermal inversion arising from dust migration.

  5. 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

  6. 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 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

  7. Hydrogen formation in PDRs: Laboratory stuides on recombinative hydrogen desorption from graphite

    NASA Astrophysics Data System (ADS)

    Baouche, Saoud; Hornekær, Liv; Petrunin, V. V.; Luntz, Alan C.; Zecho, T.; Baurichter, Arnd

    Recent laboratory studies have shown that hydrogen atoms with temperatures exceeding 2000K, corresponding to velocities higher than 0.6 Km/s, adsorb into the chemisorption state on graphite surfaces [Zecho (2002)], at conditions similar to those occuring near dissociation fronts in photo dissociation regions (PDRs) [Hollenbach, & Tielens (1999)]. In the same study it was found by thermal desorption spectroscopy that hydrogen desorbs recombinatively with first order kinetics at temperatures around 450 K on a laboratory time scale [Zecho (2002)]. The corresponding desorption energy is compatible with 1.3eV, a value derived from an elaborate density functional analysis [Sha, & Jackson (2002)]. We present and discuss results of laboratory investigations on the dynamics of the molecular hydrogen formation reaction. In our ultra high vacuum surface science apparatus, we first cover a highly oriented pyrolitically grown graphite (0001) surface (HOPG) at room temperature with hydrogen atoms from a thermal cracker type atom source (T(H)= 2000K). We then apply pulsed laser assisted associative desorption (LAAD)[Diekhoner (2001)] to measure time-of-flight distributions of hydrogen and deuterium molecules released from the surface. We find that the molecules are ejected with high translational energies into the gas phase. The translational energy distribution peaks at around 1.3eV and is about 1.0eV wide, indicating that in the extreme up to 1/2 of the recombination energy is going into the translational co-ordinate. Molecules desorbing from step edges desorb at higher temperatures but exhibit a lower translational energy component, compatible with a surface temperature Maxwell Boltzmann distribution. Angular resolved measurements show that the desorption is sharply peaked into the direction of the surface normal, the width of the distribution depending on the surface temperature and the nature of the 'launch site' (basal plane sites/ edge site). An isotope effect could not be detected within the accuracy of the experiment. Our experimental findings will be compared to theoretical analyses by density functional analysis of several groups [Sha, & Jackson (2002), Sidis (2000), Ferro et al. (2002), Miura (2003)], and will be discussed in terms of their astrochemical relevance. State resolved experiments on the energy partitioning into the remaining molecular degrees of freedom and into the energy left in the surface are in preparation.

  8. Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

    PubMed

    Tahervand, Samaneh; Jalali, Mohsen

    2016-06-01

    The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH. PMID:27147235

  9. 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.

  10. 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 3400 ng m(-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

  11. 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.

  12. Data quality in tissue analysis using desorption electrospray ionization.

    PubMed

    Dill, Allison L; Eberlin, Livia S; Costa, Anthony B; Ifa, Demian R; Cooks, R Graham

    2011-10-01

    There has been a recent surge in applications of mass spectrometry (MS) to tissue analysis, particularly lipid-based tissue imaging using ambient ionization techniques. This recent growth highlights the need to examine the effects of sample handling, storage conditions, and experimental protocols on the quality of the data obtained. Variables such as time before freezing after organ removal, storage time at -80 °C, time stored at room temperature, heating, and freeze/thaw cycles were investigated for their effect on the data quality obtained in desorption electrospray ionization (DESI)-MS using mouse brain. In addition, analytical variables such as tissue thickness, drying times, and instrumental conditions were also examined for their impact on DESI-MS data. While no immediate changes were noted in the DESI-MS lipid profiles of the mouse brain tissue after spending 1 h at room temperature when compared to being frozen immediately following removal, minor changes were noted between the tissue samples after 7 months of storage at -80 °C. In tissue sections stored at room temperature, degradation was noted in 24 h by the appearance of fatty acid dimers, which are indicative of high fatty acid concentrations, while in contrast, those sections stored at -80 °C for 7 months showed no significant degradation. Tissue sections were also subjected to up to six freeze/thaw cycles and showed increasing degradation following each cycle. In addition, tissue pieces were subjected to 50 °C temperatures and analyzed at specific time points. In as little as 2 h, degradation was observed in the form of increased fatty acid dimer formation, indicating that enzymatic processes forming free fatty acids were still active in the tissue. We have associated these dimers with high concentrations of free fatty acids present in the tissue during DESI-MS experiments. Analytical variables such as tissue thickness and time left to dry under nitrogen were also investigated, with no change in the resulting profiles at thickness from 10 to 25 μm and with optimal signal obtained after just 20 min in the dessicator. Experimental conditions such as source parameters, spray solvents, and sample surfaces are all shown to impact the quality of the data. Inter-section (relative standard deviation (%RSD), 0.44-7.2%) and intra-sample (%RSD, 4.0-8.0%) reproducibility data show the high quality information DESI-MS provides. Overall, the many variables investigated here showed DESI-MS to be a robust technique, with sample storage conditions having the most effect on the data obtained, and with unacceptable sample degradation occurring during room temperature storage. PMID:21789488

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

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

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

  15. 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...

  16. 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)

  17. 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

  18. Desorption of perylene from combustion, NaCl, and carbon particles

    SciTech Connect

    Steiner, D.; Burtscher, H.K. )

    1994-07-01

    The gas/particle distribution of perylene as a model PAH (polyaromatic hydrocarbon) is measured within a temperature range from 300 to 650 K. Perylene is adsorbed onto the core of combustion particles of different size (30- 80 nm in diameter) and origin (diesel engine and oil burner), carbon particles, and NaCl particles. The adsorbed perylene consists of a fraction x, that is nonremovable at temperatures up to 650 K and a fraction that can be desorbed at temperatures below 500 K. The mean desorption temperature T[sub 50%] (50% of perylene still in the particulate phase) and the fraction x are increasing with increasing diameter of the particles in the case of combustion particles and carbon particles. T[sub 50%] and x of the NaCl particles show no size dependence. The desorption enthalpy E[sub d] is close to the evaporation enthalpy of perylene. However, to model the experimental results by a two-step adsorption model, a distribution of E[sub d] instead of a single value has to be assumed. The results show that carbon particles may be used as a model for combustion particles when studying the adsorption of low volatile PAHs, whereas NaCl particles show considerable differences in their sorption properties. 28 refs., 11 figs., 1 tab.

  19. 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.

  20. Desorption electrospray ionization of explosives on surfaces: sensitivity and selectivity enhancement by reactive desorption electrospray ionization.

    PubMed

    Cotte-Rodríguez, Ismael; Takáts, Zoltán; Talaty, Nari; Chen, Huanwen; Cooks, R Graham

    2005-11-01

    Desorption electrospray ionization (DESI), an ambient mass spectrometry technique, is used for trace detection of the explosives trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), Pentaerythritol tetranitrate (PETN), and their plastic compositions (Composition C-4, Semtex-H, Detasheet) directly from a wide variety of surfaces (metal, plastic, paper, polymer) without sample preparation or pretreatment. Analysis of the explosives is performed under ambient conditions from virtually any surface in very short times (<5 s) including confirmatory tandem mass spectrometry (MS/MS) experiments, while retaining the sensitivity and specificity that mass spectrometry offers. Increased selectivity is obtained both by MS/MS and by performing additional experiments in which additives are included in the spray solvent. These reactive DESI experiments (reactions accompanying desorption) produce such ions as the chloride and trifluoroacetate adducts of RDX and HMX or the Meisenheimer complex of TNT. Desorption atmospheric pressure chemical ionization, a variant of DESI that uses gas-phase ions generated by atmospheric pressure corona discharges of toluene or other organic compounds, provides evidence for a heterogeneous-phase (gaseous ion/absorbed analyte) charge-transfer mechanism of DESI ionization in the case of explosives. Plastic explosives on surfaces were analyzed directly as fingerprints, without sample preparation, to test DESI as a possible method for in situ detection of explosives-contaminated surfaces. DESI also allowed detection of explosives in complex matrixes, including lubricants, household cleaners, vinegar, and diesel fuel. Absolute limits of detection for the neat explosives were subnanogram in all cases and subpicogram in the case of TNT. The DESI response was linear over 3 orders of magnitude for TNT. Quantification of RDX on paper gave a precision (RSD) of 2.3%. Pure water could be used as the spray solution for DESI, and it showed ionization efficiencies for RDX in the negative ion mode similar to that given by methanol/water. DESI represents a simple and rapid way to detect explosives in situ with high sensitivity and specificity and is especially useful when they are present in complex mixtures or in trace amounts on ordinary environmental surfaces. PMID:16255571

  1. 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.

  2. Electrospun nanofibers as substrates for surface-assisted laser desorption/ionization and matrix-enhanced surface-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Lu, Tian; Olesik, Susan V

    2013-05-01

    Electrospun polymeric nanofibers (polyacrylonitrile, poly(vinyl alcohol), and SU-8 photoresist) and carbon nanofibers pyrolyzed to final temperatures of 600, 800, and 900 °C were used as substrates for surface-assisted laser desorption/ionization (SALDI) and matrix-enhanced surface-assisted laser desorption/ionization (ME-SALDI) analyses. Sample preparation of polymeric analytes using the electrospun target plate for SALDI analysis is simple and fast. Signal enhancements for poly(ethylene glycol) were noted with nanofibrous carbon substrates compared to those obtained with commercially available stainless steel plates when no organic matrix is used. Minimal fragmentation was observed. Poly(ethylene glycol) with a molecular weight as high as 900 000 Da was successfully detected using the carbon nanofibrous substrate processed to 800 °C, which is the highest molecular weight that has been studied by SALDI. Small molecules were detected using nanofibrous carbon substrate processed to 800 °C. For example, spectra of glucose, arginine, and crystal violet were obtained with no observed interferences in the low molecular weight range. The SALDI results show enhanced shot-to-shot reproducibility compared to matrix-assisted laser desorption/ionization (MALDI). High-quality polystyrene spectra were obtained for the first time using SALDI nanofibrous polyacrylonitrile substrates. Significantly enhanced signal-to-noise ratios were obtained using ME-SALDI compared to conventional MALDI or SALDI for the studied analytes. A detection limit of 400 amol was achieved for angiotensin I using the nanofibrous carbon ME-SALDI substrate. PMID:23537004

  3. 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

  4. The influences of various factors on the adsorption-desorption behaviors of hydrophobic organic compounds in sediments of Lake Charles, LA

    SciTech Connect

    Wei Chen; Kan, A.T.; Tomson, M.B.

    1996-10-01

    Both the adsorption and the desorption processes play important roles in the transport and fate of organic contaminants in water-sediments and groundwater systems. The adsorption-desorption processes are shown to be influenced by a number of factors, including sediments organic carbon content, contaminant aqueous solubility, aqueous-phase concentration as well as some natural environmental factors such as pH, pE, ionic strength and temperature. External mechanical forces, such as sediment perturbation, and repeated dredging will also have finite effect on the microscopic interparticle forces that control bonds between large and small grain particles. The objective of this research is to study the influences of various environmental effects on the equilibrium or non-equilibrium desorption behavior of nonpolar organic pollutants in historically contaminated natural sediments of Lake Charles, LA. Differences of desorption behavior between freshly and historically contaminated sediments will be compared in order to evaluated the desorption mechanism. The influences of particle size, mineral composition, organic matter concentration, and aqueous phase matrix composition on desorption behaviour will also be evaluated.

  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. 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}.

  7. 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.

  8. 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...

  9. 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.

  10. Assessment of the high temperature fission chamber technology for the French fast reactor program

    SciTech Connect

    Jammes, C.; Filliatre, P.; Geslot, B.; Domenech, T.; Normand, S.

    2011-07-01

    High temperature fission chambers are key instruments for the control and protection of the sodium-cooled fast reactor. First, the developments of those neutron detectors, which are carried out either in France or abroad are reviewed. Second, the French realizations are assessed with the use of the technology readiness levels in order to identify tracks of improvement. (authors)

  11. 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.

  12. 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...

  13. 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.

  14. 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.

  15. Enhanced hydrogen desorption properties of magnesium hydride by coupling non-metal doping and nano-confinement

    NASA Astrophysics Data System (ADS)

    He, Daliang; Wang, Yulong; Wu, Chengzhang; Li, Qian; Ding, Weizhong; Sun, Chenghua

    2015-12-01

    Magnesium hydride (MgH2) offers excellent capacity to store hydrogen, but it suffers from the high desorption temperature (>283 °C for starting release hydrogen). In this work, we calculated the hydrogen desorption energy of Mg76H152 clusters with/without non-metal dopants by density functional theory method. Phosphorus (P), as identified as the best dopant, can reduce the reaction energy for releasing one hydrogen molecule from 0.75 eV (bulk MgH2) to 0.20 eV. Inspired by the calculation, P-doped ordered mesoporous carbon (CMK-3) was synthesized by one-step method and employed as the scaffold for loading MgH2 nanoparticles, forming MgH2@P/CMK-3. Element analysis shows that phosphorus dopants have been incorporated into the CMK-3 scaffold and magnesium and phosphorus elements are well-distributed in carbon scaffold hosts. Tests of hydrogen desorption confirmed that P-doping can remarkably enhance the hydrogen release properties of nanoconfined MgH2 at low temperature, specifically ˜1.5 wt. % H2 released from MgH2@P/CMK-3 below 200 °C. This work, based on the combination of computational calculations and experimental studies, demonstrated that the combined approach of non-metal doping and nano-confinement is promising for enhancing the hydrogen desorption properties of MgH2, which provides a strategy to address the challenge of hydrogen desorption from MgH2 at mild operational conditions.

  16. 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.

  17. 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.

  18. Peptide desorption kinetics from single molecule force spectroscopy studies.

    PubMed

    Krysiak, Stefanie; Liese, Susanne; Netz, Roland R; Hugel, Thorsten

    2014-01-15

    We use a combined experimental/theoretical approach to determine the intrinsic monomeric desorption rate k0 of polytyrosine and polylysine homopeptides from flat surfaces. To this end, single polypeptide molecules are covalently attached to an AFM cantilever tip and desorbed from hydrophobic self-assembled monolayers in two complementary experimental protocols. In the constant-pulling-velocity protocol, the cantilever is moved at finite velocity away from the surface and the distance at which the constant plateau force regime ends and the polymer detaches is recorded. In the waiting-time protocol, the cantilever is held at a fixed distance above the surface and the time until the polymer detaches is recorded. The desorption plateau force is varied between 10 and 90 pN, by systematically changing the aqueous solvent quality via the addition of ethanol or salt. A simultaneous fit of the experimental data from both protocols with simple two-state kinetic polymer theory allows to unambiguously disentangle and determine the model parameters corresponding to polymer contour length L, Kuhn length a, adsorption free energy λ, and intrinsic monomeric desorption rate k0. Crucial to our analysis is that a statistically significant number of single-polymer desorption experiments are done with one and the same single polymer molecule for different solvent qualities. The surprisingly low value of about k0 ≈ 10(5) Hz points to significant cooperativity in the desorption process of single polymers. PMID:24328353

  19. 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.

  20. Adsorption, thermal reaction, and desorption of disilane on Ge(111)-[ital c](2[times]8)

    SciTech Connect

    Lin, D.; Hirschorn, E.S.; Miller, T.; Chiang, T. Materials Research Laboratory, University of Illinois, 104 South Goodwin Avenue, Urbana, Illinois 61801-2902 )

    1994-01-15

    Room-temperature adsorption of disilane (Si[sub 2]H[sub 6]) on Ge(111)-[ital c](2[times]8) and subsequent thermal reactions and desorption at elevated temperatures were studied using scanning tunneling microscopy and core-level photoemission. The initial adsorption results in the formation of various surface radicals, and the reacted areas on the surface grow laterally for increasing exposures. The sticking coefficient is rather low, and an exposure greater than about 30 000 langmuirs is needed to saturate the surface. The net amount of Si deposited for the saturated surface is about one-half of an atomic layer. Thermal annealing causes the hydrogen atoms to desorb and the Si atoms to move below the surface. For annealing temperatures beyond about 630 K, the desorption of hydrogen becomes complete, all of the Si atoms move below the surface, and the resulting surface resembles the starting clean Ge(111)-[ital c](2[times]8) surface except that the [ital c](2[times]8) long-range order is partially destroyed. Step flow and island coarsening, similar to growth by molecular-beam epitaxy, are observed.

  1. 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.

  2. 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.

  3. 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.

  4. 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)

    Öberg, H.; Gladh, J.; Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Föhlisch, A.; Katayama, T.; Kaya, S.; LaRue, J.; Møgelhøj, A.; Nordlund, D.; Ogasawara, H.; Schlotter, W. F.; Sellberg, J. A.; Sorgenfrei, F.; Turner, J. J.; Wolf, M.; Wurth, W.; Öström, H.; Nilsson, A.; Nørskov, 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.

  5. 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.

  6. Flash desorption/mass spectrometry for the analysis of less- and nonvolatile samples using a linearly driven heated metal filament.

    PubMed

    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 ~10(4) °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 ᅟ PMID:23982934

  7. 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.

  8. Lateral hopping and desorption of a single CO molecule on a Cu(110) surface induced by femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Ueba, H.; Ootsuka, Y.

    2013-05-01

    Lateral hopping and desorption of a single CO molecule on a Cu(110) surface [Bartels , ScienceSCIEAS0036-807510.1126/science.1099770 305, 648 (2004)] induced by femtosecond laser pulses are studied using an indirect heat-transfer model. In addition to a direct heating of the reaction coordinate (RC) mode [frustrated translation (FT) mode for hopping and center-of-mass (CM) mode for desorption] by laser-generated hot electrons in the substrate, we consider an indirect heating of the RC mode through intermode coupling between the frustrated rotation (FR) mode and the RC mode. We calculate the transient behavior of the effective temperature of the FT and the CM modes, and of the normalized reaction yield. The experimental result of a ratio of the hopping yield along and across a row on a Cu(110) surface is nicely calculated. Although no information is available for the attempt frequency in a form of the Arrhenius equation for thermally activated reactions, it is predicted under which condition the desorption rate becomes in the same order of magnitude as the hopping rate, although the barrier height for desorption is much higher than for hopping. The present analysis highlights the role of excitation of the FR mode in reactions of a CO molecule as has been confirmed in the real-time observation [Backus , ScienceSCIEAS0036-807510.1126/science.1120693 310, 1790 (2005)].

  9. 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.

  10. 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.

  11. 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

  12. 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…

  13. 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.

  14. 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.

  15. 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.

  16. Smoothness and cleanliness of the GaAs (100) surface after thermal desorption of the native oxide for the synthesis of high mobility structures using molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Lee, J. J. D.; West, K. W.; Baldwin, K. W.; Pfeiffer, L. N.

    2012-10-01

    To prepare a GaAs substrate for molecular beam epitaxial (MBE) growth, the nominal ˜3 nm native oxide is typically thermally desorbed into vacuum. To test the completeness and quality of this desorption, we describe a technique, which combines MBE, thermal desorption, atomic force microscopy (AFM), reflection high-energy electron diffraction (RHEED), and secondary ion mass spectroscopy (SIMS), for detecting roughness and trace residues of contamination on (100) GaAs surfaces before MBE growth. At all desorption temperatures in the range 600-665 °C, our RHEED measurements show that the native oxide is largely desorbed within 4 min. However, the SIMS and AFM data indicate that a residue of carbon invariably remains on the GaAs (100) surface, and tenaciously resists all further attempts at its removal by thermal desorption. Since thermal desorption of the native oxide has long been the standard technique for preparing GaAs substrates for MBE growth, we suggest that MBE growth on GaAs has in general been accomplished by epitaxially growing through a partial monolayer of carbon. We believe this is the likely reason for the generally unsatisfactory quality of GaAs MBE growth after lithographic patterning on previously MBE grown structures. Our AFM data also indicate that extended native oxide desorption times or high desorption temperatures not only are ineffective at removal of the carbon residue, but are always accompanied by additional strong roughening effects on the GaAs surface morphology. Finally, we demonstrate that smoother starting surfaces for MBE growth correlate well with higher two-dimensional carrier mobilities in the resulting AlGaAs/GaAs heterostructures.

  17. 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.

  18. 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

  19. Sorption and desorption of sulfentrazone in Brazilian soils.

    PubMed

    Passos, Ana Beatriz R J; Freitas, Marco Antonio M; Torres, Lívia G; Silva, Antonio A; Queiroz, Maria Eliana L R; Lima, Cláudio F

    2013-01-01

    This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops. PMID:23638891

  20. Coverage dependent desorption dynamics of deuterium on Si(100) surfaces: interpretation with a diffusion-promoted desorption model.

    PubMed

    Matsuno, T; Niida, T; Tsurumaki, H; Namiki, A

    2005-01-01

    We studied coverage dependence of time-of-flight (TOF) spectra of D2 molecules thermally desorbed from the D/Si(100) surface. The mean translational energies Et of desorbed D2 molecules were found to increase from 0.20+/-0.05 eV to 0.40+/-0.04 eV as the desorption coverage window was decreased from 1.0 ML> or =thetaD> or =0.9 ML to 0.2 ML> or =thetaD> or =0 ML, being consistent with the kinetics switch predicted in the interdimer mechanism. The measured TOF spectra were deconvoluted into 2H, 3H, and 4H components by a curve fitting method along the principle of detailed balance. As a result, it turned out that the desorption kinetics changes from the 4H to the 3H situation at high coverage above thetaD=0.9 ML, while the 2H desorption is dominant for a quite wide coverage region up to thetaD=0.8 ML. A dynamic desorption mechanism by which the desorption is promoted by D-atom diffusion to dangling bonds was proposed. PMID:15638609

  1. High-temperature gas-cooled reactor (HTGR): long term program plan

    SciTech Connect

    Not Available

    1980-10-09

    The FY 1980 effort was to investigate four technology options identified by program participants as potentially viable candidates for near-term demonstration: the Gas Turbine system (HTGR-GT), reflecting its perceived compatibility with the dry-cooling market, two systems addressing the process heat market, the Reforming (HTGR-R) and Steam Cycle (HTGR-SC) systems, and a more developmental reactor system, The Nuclear Heat Source Demonstration Reactor (NHSDR), which was to serve as a basis for both the HTGR-GT and HTGR-R systems as well as the further potential for developing advanced applications such as steam-coal gasification and water splitting.

  2. Laser desorption postionization mass spectrometry imaging of biological targets.

    PubMed

    Akhmetov, Artem; Bhardwaj, Chhavi; Hanley, Luke

    2015-01-01

    Laser desorption photoionization mass spectrometry (LDPI-MS) utilizes two separate light sources for desorption and photoionization of species from a solid surface. This technique has been applied to study a wide variety of molecular analytes in biological systems, but is not yet available in commercial instruments. For this reason, a generalized protocol is presented here for the use of LDPI-MS imaging to detect small molecules within intact biological samples. Examples are provided here for LDPI-MS imaging of an antibiotic within a tooth root canal and a metabolite within a coculture bacterial biofilm. PMID:25361678

  3. 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.

  4. Heavy-ion induced electronic desorption of gas from metals

    SciTech Connect

    Molvik, A W; Kollmus, H; Mahner, E; Covo, M K; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Kramer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2006-12-19

    During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/d/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  5. Heavy-Ion-Induced Electronic Desorption of Gas from Metals

    SciTech Connect

    Molvik, A. W.; Covo, M. Kireeff; Westenskow, G.; Kollmus, H.; Bellachioma, M. C.; Bender, M.; Kraemer, A.; Mahner, E.; Bieniosek, F. M.; Kwan, J.; Seidl, P. A.; Hedlund, E.; Westerberg, L.; Malyshev, O. B.; Prost, L.

    2007-02-09

    During heavy-ion operation in several particle accelerators worldwide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion-induced gas desorption scales with the electronic energy loss (dE{sub e}/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  6. Comparison of different substrates for laser-induced electron transfer desorption/ionization of metal complexes

    NASA Astrophysics Data System (ADS)

    Grechnikov, A. A.; Georgieva, V. B.; Donkov, N.; Borodkov, A. S.; Pento, A. V.; Raicheva, Z. G.; Yordanov, Tc A.

    2016-03-01

    Four different substrates, namely, graphite, tungsten, amorphous silicon (α-Si) and titanium dioxide (TiO2) films, were compared in view of the laser-induced electron transfer desorption/ionization (LETDI) of metal coordination complexes. A rhenium complex with 8-mercaptoquinoline, a copper complex with diphenylthiocarbazone and chlorophyll A were studied as the test analytes. The dependencies of the ion yield and the surface temperature on the incident radiation fluence were investigated experimentally and theoretically. The temperature was estimated using the numerical solution of a one-dimensional heat conduction problem with a heat source distributed in time and space. It was found that at the same temperature, the ion yield from the different substrates varies in the range of three orders of magnitude. The direct comparison of all studied substrates revealed that LETDI from the TiO2 and α-Si films offer a better choice for producing molecular ions of metal coordination complexes.

  7. 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

  8. DNASynth: A Computer Program for Assembly of Artificial Gene Parts in Decreasing Temperature

    PubMed Central

    Nowak, Robert M.; Wojtowicz-Krawiec, Anna; Plucienniczak, Andrzej

    2015-01-01

    Artificial gene synthesis requires consideration of nucleotide sequence development as well as long DNA molecule assembly protocols. The nucleotide sequence of the molecule must meet many conditions including particular preferences of the host organism for certain codons, avoidance of specific regulatory subsequences, and a lack of secondary structures that inhibit expression. The chemical synthesis of DNA molecule has limitations in terms of strand length; thus, the creation of artificial genes requires the assembly of long DNA molecules from shorter fragments. In the approach presented, the algorithm and the computer program address both tasks: developing the optimal nucleotide sequence to encode a given peptide for a given host organism and determining the long DNA assembly protocol. These tasks are closely connected; a change in codon usage may lead to changes in the optimal assembly protocol, and the lack of a simple assembly protocol may be addressed by changing the nucleotide sequence. The computer program presented in this study was tested with real data from an experiment in a wet biological laboratory to synthesize a peptide. The benefit of the presented algorithm and its application is the shorter time, compared to polymerase cycling assembly, needed to produce a ready synthetic gene. PMID:25629047

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. Desorption of vanadium oxychloride and hydrogen chloride from the pores of vanadium-modified silica gel

    SciTech Connect

    Malygin, A.A.; Dergachev, V.F.

    1988-11-20

    We report the results of a study of removal of excess unreacted vanadium oxychloride and hydrogen chloride from vanadium-containing silica gel. With the aim of accelerating the removal of traces of VOCl/sub 3/ and HCl from the pores of indicator silica gel, we carried out experiments with the use of a mixtures of water vapor and air as the desorbent stream at elevated temperatures. By conducting desorption of vanadium oxychloride and hydrogen chloride by humid air in the temperature range 573-873 K this stage and the whole process of vanadium-containing silica gel production can be accelerated considerably. Presumably, in selection of the procedure in the desorption stage it is advisable first to remove part of the unreacted vanadium oxychloride and of the reaction product (hydrogen chloride) by passing a stream of dry carrier gas for about 900 sec. After this, VOCl/sub 3/ and HC1 can be desorbed completely by passing the vapor-air mixture for 1800 sec at 573K.

  14. 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

  15. Temperature based daily incoming solar radiation modeling based on gene expression programming, neuro-fuzzy and neural network computing techniques.

    NASA Astrophysics Data System (ADS)

    Landeras, G.; López, J. J.; Kisi, O.; Shiri, J.

    2012-04-01

    The correct observation/estimation of surface incoming solar radiation (RS) is very important for many agricultural, meteorological and hydrological related applications. While most weather stations are provided with sensors for air temperature detection, the presence of sensors necessary for the detection of solar radiation is not so habitual and the data quality provided by them is sometimes poor. In these cases it is necessary to estimate this variable. Temperature based modeling procedures are reported in this study for estimating daily incoming solar radiation by using Gene Expression Programming (GEP) for the first time, and other artificial intelligence models such as Artificial Neural Networks (ANNs), and Adaptive Neuro-Fuzzy Inference System (ANFIS). Traditional temperature based solar radiation equations were also included in this study and compared with artificial intelligence based approaches. Root mean square error (RMSE), mean absolute error (MAE) RMSE-based skill score (SSRMSE), MAE-based skill score (SSMAE) and r2 criterion of Nash and Sutcliffe criteria were used to assess the models' performances. An ANN (a four-input multilayer perceptron with ten neurons in the hidden layer) presented the best performance among the studied models (2.93 MJ m-2 d-1 of RMSE). A four-input ANFIS model revealed as an interesting alternative to ANNs (3.14 MJ m-2 d-1 of RMSE). Very limited number of studies has been done on estimation of solar radiation based on ANFIS, and the present one demonstrated the ability of ANFIS to model solar radiation based on temperatures and extraterrestrial radiation. By the way this study demonstrated, for the first time, the ability of GEP models to model solar radiation based on daily atmospheric variables. Despite the accuracy of GEP models was slightly lower than the ANFIS and ANN models the genetic programming models (i.e., GEP) are superior to other artificial intelligence models in giving a simple explicit equation for the phenomenon which shows the relationship between the input and output parameters. This study provided new alternatives for solar radiation estimation based on temperatures.

  16. Using temperature-programmed reaction for kinetic analysis of reactions in dilute aqueous solutions at high pressure

    SciTech Connect

    Brown, L.F.; Robinson, B.A.

    1986-01-01

    The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs.

  17. 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.

  18. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Ma, Qingxin

    2008-04-01

    The experimental determination of rate constants for atmospheric reactions and how these rate constants vary with temperature remain a crucially important part of atmosphere science. In this study, the temperature dependence of the heterogeneous reaction of carbonyl sulfide (COS) on magnesium oxide (MgO) has been investigated using a Knudsen cell reactor and a temperature-programmed reaction apparatus. We found that the adsorption and the heterogeneous reaction are sensitive to temperature. The initial uptake coefficients (gammat(Ini)) of COS on MgO decrease from 1.07 +/- 0.71 x 10-6 to 4.84 +/- 0.60 x 10-7 with the increasing of temperature from 228 to 300 K, and the steady state uptake coefficients (gammat(SS)) increase from 5.31 +/- 0.06 x 10-8 to 1.68 +/- 0.41 x 10-7 with the increasing of temperature from 240 to 300 K. The desorption rate constants (kdes) were also found to increase slightly with the enhancement of temperature. The empirical formula between the uptake coefficients, desorption rate constants and temperature described in the form of Arrhenius expression were obtained. The activation energies for the heterogeneous reaction and desorption of COS on MgO were measured to be 11.02 +/- 0.34 kJ.mol-1 and 6.30 +/- 0.81 kJ.mol-1, respectively. The results demonstrate that the initial uptake of COS on MgO is mainly contributed by an adsorption process and the steady state uptake is due to a catalytic reaction. The environmental implication was also discussed. PMID:18302353

  19. 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.

  20. 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...

  1. 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...

  2. 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...

  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. he processed solids are either replaced f...

  4. 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.

  5. 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 ...

  6. 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...

  7. 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...

  8. Adsorption and laser-induced desorption of dimethylcadmium from silicon

    NASA Astrophysics Data System (ADS)

    Simonov, Alexander P.; Varakin, Vladimir N.

    1990-10-01

    The dynamics of Cd (cH ) 2 chemisorption and spontaneous decomposit ion on n-type 51(100) with native surface oxide the pathwa and efficiencies of the adsorbate desorption due to the absorption of the XeC1 laser radiation by silicon have been examined using laser-induced desorption miss spectrorrtry (LIDMS ) . The k inetics of these sur face processes has been found to depend on the preceding laser irradiation of the surface. The extremely fast chemisorption and efficient decomposition of the parent rrlecules have been observed on the irradiated silicon surface. The competition between intact dissociative and recombination desorption pathways was responsible for the observed laser fluence dependences of the desorption of Cd(CI-6) and i ts fragments. 1 . INTROOIJCTIct4 1 . 1 . Laser chemical vapour depos ition (LCVD). Laser-induced deposition of thin filme on solid surfaces by using volatile organometallic precursors has been the subject of numerous investigations in the 8Os2. Due to the spatial/temporal localization of laser radiation and the resonant nature of laser-rr1ecule interaction this deposition technique has such attractive features as submicrometer resolution of deposits high film growth rate and high quality lowtemperature processing. The deposition process can be controlled by varying the laser parameters (wavelength fluence beam spot on the substrate surface scanning speed ). A var iety of mater ials can be depos I ted using LCVD. Of special interest for microelectronics is the deposition of

  9. 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.

  10. 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.

  11. Nitrate sorption and desorption in biochars from fast pyrolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Increasing the nitrate (NO3-) sorption capacity of Midwestern US soils has the potential to reduce nitrate leaching to ground water and reduce the extent of the hypoxia zone in the Gulf of Mexico. The objective of this study was to determine the sorption and desorption capacity of non-activated and ...

  12. 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...

  13. 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...

  14. 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...

  15. SORPTION AND DESORPTION OF PHOSPHORUS AND NITROGEN BY CROP RESIDUE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Information concerning the ability of crop residue materials to sorb or desorb nutrients contained in runoff is limited. This laboratory study was conducted to measure sorption and desorption of inorganic nutrients by corn (Zea Mays L.), soybean (Glycine max (L.) Merr.) and winter wheat (Triticum ae...

  16. 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 ...

  17. 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...

  18. 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.

  19. 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.

  20. Experimental study of water desorption isotherms and thin-layer convective drying kinetics of bay laurel leaves

    NASA Astrophysics Data System (ADS)

    Ghnimi, Thouraya; Hassini, Lamine; Bagane, Mohamed

    2016-02-01

    The aim of this work is to determine the desorption isotherms and the drying kinetics of bay laurel leaves (Laurus Nobilis L.). The desorption isotherms were performed at three temperature levels: 50, 60 and 70 °C and at water activity ranging from 0.057 to 0.88 using the statistic gravimetric method. Five sorption models were used to fit desorption experimental isotherm data. It was found that Kuhn model offers the best fitting of experimental moisture isotherms in the mentioned investigated ranges of temperature and water activity. The Net isosteric heat of water desorption was evaluated using The Clausius-Clapeyron equation and was then best correlated to equilibrium moisture content by the empirical Tsami's equation. Thin layer convective drying curves of bay laurel leaves were obtained for temperatures of 45, 50, 60 and 70 °C, relative humidity of 5, 15, 30 and 45 % and air velocities of 1, 1.5 and 2 m/s. A non linear regression procedure of Levenberg-Marquardt was used to fit drying curves with five semi empirical mathematical models available in the literature, The R2 and χ2 were used to evaluate the goodness of fit of models to data. Based on the experimental drying curves the drying characteristic curve (DCC) has been established and fitted with a third degree polynomial function. It was found that the Midilli Kucuk model was the best semi-empirical model describing thin layer drying kinetics of bay laurel leaves. The bay laurel leaves effective moisture diffusivity and activation energy were also identified.

  1. 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.

  2. 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...

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Carriers reactivation in p+-type porous silicon accompanies hydrogen desorption

    NASA Astrophysics Data System (ADS)

    Rivolo, P.; Geobaldo, F.; Salvador, G. P.; Pallavidino, L.; Ugliengo, P.; Garrone, E.

    2005-06-01

    FTIR spectra of p+-type mesoporous silicon (m-PS) outgassed in the 300-600 K range show a loss of transparency with increasing temperature, more pronounced at low frequencies. This is evidence of free-carrier formation. Previous work (F. Geobaldo et al., Sensors and Actuators B, in press [1]) concerning the reversible interaction of NO2 and NH3 has shown the presence at the surface of adsorption sites involving Si/B pairs. Thermal treatment of the sample causes desorption of molecular hydrogen, released through the homolytic splitting of Si-H bonds. Besides meeting each other forming a H2 molecule, H atoms may interact with an adsorption site, by creating a new H-Si-B bond. This new bond needs one additional electron to be formed and injection of a hole takes place into the solid. At higher temperatures, surface hydrogen is almost totally removed and the sample transparency recovered.

  8. 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)

  9. 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

  10. A possible answer to the mysterious non-detection of hydroxylamine in space: the thermal desorption mechanism

    NASA Astrophysics Data System (ADS)

    Jonusas, Mindaugas; Krim, Lahouari

    2016-06-01

    The presence of NH2OH, one of the main precursors in the formation of amino-acids, on dust grain mantles, may be the most obvious elucidation for the creation of large pre-biotic molecules in the interstellar medium. However, while many laboratory experimental studies, to simulate the icy grain chemistry in space, found that NH2OH molecules may be easily formed in solid phase with high abundances and then they should desorb, through a temperature-induced desorption into the gas phase, with the same high abundances; all the spatial observations conclude that NH2OH is not detected in gas phase within any of the explored astronomical sources. Such inconsistencies between laboratory experiment simulations and spatial observations lead our investigations towards this experimental study to see if there is any chemical transformation of NH2OH, occurring in the solid phase before the desorption processes of NH2OH from the mantle of interstellar icy grains. Our experimental results show that the heating of NH2OH-H2O ices lead to a decomposition of NH2OH into HNO, NH3 and O2, even before reaching its desorption temperature. We show through this work that the NH2OH non-detection from previous examined astronomical sources could mainly due to its high reactivity in solid phase on the icy interstellar grains.

  11. Correlation of Chemisorption and Electronic Effects for Metal Oxide Interfaces: Transducing Principles for Temperature Programmed Gas Microsensors (Final Report)

    SciTech Connect

    S. Semancik; R. E. Cavicchi; D. L. DeVoe; T. J. McAvoy |

    2001-12-21

    This Final Report describes efforts and results for a 3-year DoE/OST-EMSP project centered at NIST. The multidisciplinary project investigated scientific and technical concepts critical for developing tunable, MEMS-based, gas and vapor microsensors that could be applied for monitoring the types of multiple analytes (and differing backgrounds) encountered at DoE waste sites. Micromachined ''microhotplate'' arrays were used as platforms for fabricating conductometric sensor prototypes, and as microscale research tools. Efficient microarray techniques were developed for locally depositing and then performance evaluating thin oxide films, in order to correlate gas sensing characteristics with properties including composition, microstructure, thickness and surface modification. This approach produced temperature-dependent databases on the sensitivities of sensing materials to varied analytes (in air) which enable application-specific tuning of microsensor arrays. Mechanistic studies on adsorb ate transient phenomena were conducted to better understand the ways in which rapid temperature programming schedules can be used to produce unique response signatures and increase information density in microsensor signals. Chemometric and neural network analyses were also employed in our studies for recognition and quantification of target analytes.

  12. Determination of organic sulfur forms in some coals and kerogens by atmospheric pressure temperature programmed reduction (AP-TPR)

    SciTech Connect

    Yperman, J.; Maes, I.I.; Franco, D.

    1995-12-31

    The following samples have been investigated as examples for the applicability of the atmospheric pressure temperature programmed reduction (AP-TPR) technique: Indiana No. 5, Herrin No. 6, and Upper-Freeport (Argonne Premium coal, USA), Kimmeridge Dorset-Cuddle (Type II kerogen, UK) and Mequinenza (lignite, Spain). The Mequinenza lignite has been treated with diluted nitric acid in order to remove pyrite while for the Upper Freeport and the Kimmeridge the pyrite was removed by a LiAlH{sub 4} treatment. The Indiana No. 5 and Herrin No. 6 were treated with a peroxy-acetic acid solution at room temperature in order to remove beside pyrite also other sulfur groups. The AP-TPR profiles of the treated and untreated samples are discussed and compared with each other. It is demonstrated that LiAlH{sub 4} as the peroxide treatment not only removes pyrite, but also changes and removes other sulfur functionalities. The AP-TPR technique proved that the pyrite signal is clearly resolved and that possible retrogressive reactions might be hidden under other sulfur functionalities, which has no important influence on the interpretation of the AP-TPR profile after pyrite reduction.

  13. Simultaneous desorption behavior of M borohydrides and Mg2FeH6 reactive hydride composites (M = Mg, then Li, Na, K, Ca)

    NASA Astrophysics Data System (ADS)

    Chaudhary, Anna-Lisa; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Deledda, Stefano; Sørby, Magnus H.; Hauback, Bjørn C.; Pistidda, Claudio; Klassen, Thomas; Dornheim, Martin

    2015-08-01

    Combinations of complex metal borohydrides ball milled with the transition metal complex hydride, Mg2FeH6, are analysed and compared. Initially, the Reactive Hydride Composite (RHC) of Mg2+ cation mixtures of Mg2FeH6 and γ-Mg(BH4)2 is combined in a range of molar ratios and heated to a maximum of 450 °C. For the molar ratio of 6 Mg2FeH6 + Mg(BH4)2, simultaneous desorption of the two hydrides occurred, which resulted in a single event of hydrogen release. This single step desorption occurred at temperatures between those of Mg2FeH6 and γ-Mg(BH4)2. Keeping this anionic ratio constant, the desorption behavior of four other borohydrides, Li-, Na-, K-, and Ca-borohydrides was studied by using materials ball milled with Mg2FeH6 applying the same milling parameters. The mixtures containing Mg-, Li-, and Ca-borohydrides also released hydrogen in a single event. The Mass Spectrometry (MS) results show a double step reaction within a narrow temperature range for both the Na- and K-borohydride mixtures. This phenomenon, observed for the RHC systems at the same anionic ratio with all five light metal borohydride mixtures, can be described as simultaneous hydrogen desorption within a narrow temperature range centered around 300 °C.

  14. 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.

  15. Bulk Diffusion-Controlled Thermal Desorption Spectroscopy with Examples for Hydrogen in Iron

    NASA Astrophysics Data System (ADS)

    Kirchheim, Reiner

    2016-02-01

    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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. Analysis of organic compounds in water by direct adsorption and thermal desorption. [Dissertation

    SciTech Connect

    Ryan, J.P. Jr.

    1980-03-01

    An instrument was designed and constructed that makes it possible to thermally desorb organic compounds from wet adsorption traps to a gas chromatograph in an efficient and reproducible manner. Based on this device, a method of analyzing organics in water was developed that is rapid, sensitive, and of broader scope than previously published methods. The system was applied to the analysis of compounds with a wide range of volatilities. Temperature and flow parameters were investigated and specific procedures for quantitation were established. Real samples, including tap water and well water, were also analyzed with this system. Depending on the analysis requirements, the thermal desorption instrument can be used with either packed column or high resolution open-tubular column gas chromatography. The construction plans of normal and high-resolution systems are presented along with chromatograms and data produced by each. Finally, an improved thermal desorption instrument is described. Modifications to the basic system, including splitless injection onto a capillary column, automation, dual cryogenic trapping, reduction of scale, and effluent splitting to dual detection are discussed at length as they relate to the improved instrument.

  1. 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

  2. Spatially resolved thermal desorption/ionization coupled with mass spectrometry

    DOEpatents

    Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S

    2013-02-26

    A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.

  3. Adsorption-desorption kinetics of surfactants at liquid surfaces.

    PubMed

    He, Yunfei; Yazhgur, Pavel; Salonen, Anniina; Langevin, Dominique

    2015-08-01

    The paper discusses adsorption and desorption energy barriers for macroscopic interfaces of surfactant solutions. Literature data suggest that adsorption and desorption are not always fully diffusion controlled. Apart from electrostatic barriers that lead to strong deviations, other types of barriers are less easy to identify, because smaller deviations from diffusion controlled mechanisms are evidenced. Complete models involving both diffusion and sorption barriers are very complex and involve many adjustable parameters, making the data analysis frequently unreliable. Empirical equations of state are used in most cases, although they are inaccurate, especially close to the cmc. The variation of sorption energies with surface concentration is not accurately described in the models. Finally, convection can mask the effect of sorption energy barriers. Experiments are presented to illustrate the main difficulties encountered. PMID:25307125

  4. Improved Imaging Resolution in Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    Imaging resolution of desorption electrospray ionization mass spectrometry (DESI-MS) was investigated using printed patterns on paper and thin-layer chromatography (TLC) plate surfaces. Resolution approaching 40 m was achieved with a typical DESI-MS setup, which is approximately 5 times better than the best resolution reported previously. This improvement was accomplished with careful control of operational parameters (particularly spray tip-to-surface distance, solvent flow rate, and spacing of lane scans). Also, an appropriately strong analyte/surface interaction and uniform surface texture on the size scale no larger that the desired imaging resolution were required to achieve this resolution. Overall, conditions providing the smallest possible effective desorption/ionization area in the DESI impact plume region and minimizing the analyte redistribution on the surface during analysis led to the improved DESI-MS imaging resolution.

  5. Laser desorption in an ion trap mass spectrometer

    SciTech Connect

    Eiden, G.C.; Cisper, M.E.; Alexander, M.L.; Hemberger, P.H.; Nogar, N.S.

    1993-02-01

    Laser desorption in a ion-trap mass spectrometer shows significant promise for both qualitative and trace analysis. Several aspects of this methodology are discussed in this work. We previously demonstrated the generation of both negative and positive ions by laser desorption directly within a quadrupole ion trap. In the present work, we explore various combinations of d.c., r.f., and time-varying fields in order to optimize laser generated signals. In addition, we report on the application of this method to analyze samples containing compounds such as amines, metal complexes, carbon clusters, and polynuclear aromatic hydrocarbons. In some cases the ability to rapidly switch between positive and negative ion modes provides sufficient specificity to distinguish different compounds of a mixture with a single stage of mass spectrometry. In other experiments, we combined intensity variation studies with tandem mass spectrometry experiments and positive and negative ion detection to further enhance specificity.

  6. Thin layer chromatography--mass spectrometry using infrared lase desorption

    NASA Astrophysics Data System (ADS)

    Fanibanda, Tanaz; Milnes, John; Gormally, John

    1994-12-01

    The infrared laser desorption of the drug naproxen from silica thin layer chromatography (TLC) plates is described. Desorbed neutral molecules were ionized by two-photon ionization at a wavelength of 266 nm and mass spectra were recorded using a time-of-flight mass spectrometer. Particular features investigated were the sensitivity attainable and the effect of repeated irradiation of the same area of the TLC plate.

  7. Study on adsorption and desorption of ammonia on graphene.

    PubMed

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-12-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak. PMID:26377212

  8. Increasing ion sorption and desorption rates of conductive electrodes

    DOEpatents

    DePaoli, David William; Kiggans, Jr., James O; Tsouris, Costas; Bourcier, William; Campbell, Robert; Mayes, Richard T

    2014-12-30

    An electrolyte system includes a reactor having a pair of electrodes that may sorb ions from an electrolyte. The electrolyte system also includes at least one power supply in electrical communication with the reactor. The at least one power supply may supply a DC signal and an AC signal to the pair of electrodes during sorption of the ions. In addition, the power supply may supply only the AC signal to the pair of electrodes during desorption of the ions.

  9. Study on adsorption and desorption of ammonia on graphene

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-09-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak.

  10. Laser desorption/ionization of single ultrafine multicomponent aerosols

    SciTech Connect

    Ge, Z.; Wexler, A.S.; Johnston, M.V.

    1998-10-15

    Laser desorption/ionization characteristics of single ultrafine multicomponent aerosols have been investigated. A simple model is developed to quantify the relationship between ion yield and particle composition. Using this model, a relative ion yield and particle composition. Using this model, a relative ion yield of 4.9 is found for K{sup +} from KCl over Na{sup +} from NaCl, while 4.4 is found for Na{sup +} from NaCl over NO{sup +} from NH{sub 4}NO{sub 3}. It has been shown that analyzing particles composed of chemicals with common cations but different anions, such as NaCl/NaNO{sub 3} from positive ion spectra, is also possible. The ability of laser desorption/ionization to detect trace metals (sodium, magnesium, potassium, chromium, iron, copper, zinc, cadmium, cesium, lanthanum, and lead) is studied. The application of laser desorption/ionization to measuring atmospheric ultrafine aerosols is also discussed.

  11. Adsorption-desorption kinetics of soft particles onto surfaces

    NASA Astrophysics Data System (ADS)

    Osberg, Brendan; Gerland, Ulrich

    A broad range of physical, chemical, and biological systems feature processes in which particles randomly adsorb on a substrate. Theoretical models usually assume ``hard'' (mutually impenetrable) particles, but in soft matter physics the adsorbing particles can be effectively compressible, implying ``soft'' interaction potentials. We recently studied the kinetics of such soft particles adsorbing onto one-dimensional substrates, identifying three novel phenomena: (i) a gradual density increase, or ''cramming'', replaces the usual jamming behavior of hard particles, (ii) a density overshoot, can occur (only for soft particles) on a time scale set by the desorption rate, and (iii) relaxation rates of soft particles increase with particle size (on a lattice), while hard particles show the opposite trend. The latter occurs since unjamming requires desorption and many-bodied reorganization to equilibrate -a process that is generally very slow. Here we extend this analysis to a two-dimensional substrate, focusing on the question of whether the adsorption-desorption kinetics of particles in two dimensions is similarly enriched by the introduction of soft interactions. Application to experiments, for example the adsorption of fibrinogen on two-dimensional surfaces, will be discussed.

  12. Unexpected Analyte Oxidation during Desorption Electrospray Ionization - Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a result of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.

  13. The desorptivity model of bulk soil-water evaporation

    NASA Technical Reports Server (NTRS)

    Clapp, R. B.

    1983-01-01

    Available models of bulk evaporation from a bare-surfaced soil are difficult to apply to field conditions where evaporation is complicated by two main factors: rate-limiting climatic conditions and redistribution of soil moisture following infiltration. Both factors are included in the "desorptivity model', wherein the evaporation rate during the second stage (the soil-limiting stage) of evaporation is related to the desorptivity parameter, A. Analytical approximations for A are presented. The approximations are independent of the surface soil moisture. However, calculations using the approximations indicate that both soil texture and soil moisture content at depth significantly affect A. Because the moisture content at depth decreases in time during redistribution, it follows that the A parameter also changes with time. Consequently, a method to calculate a representative value of A was developed. When applied to field data, the desorptivity model estimated cumulative evaporation well. The model is easy to calculate, but its usefulness is limited because it requires an independent estimate of the time of transition between the first and second stages of evaporation. The model shows that bulk evaporation after the transition to the second stage is largely independent of climatic conditions.

  14. Fate of mercury in flue gas desulfurization gypsum determined by Temperature Programmed Decomposition and Sequential Chemical Extraction.

    PubMed

    Zhu, Zhenwu; Zhuo, Yuqun; Fan, Yaming; Wang, Zhipeng

    2016-05-01

    A considerable amount of Hg is retained in flue gas desulfurization (FGD) gypsum from Wet Flue Gas Desulfurization (WFGD) systems. For this reason, it is important to determine the species of Hg in FGD gypsum not only to understand the mechanism of Hg removal by WFGD systems but also to determine the final fate of Hg when FGD gypsum is disposed. In this study, Temperature Programmed Decomposition (TPD) and Sequential Chemical Extraction (SCE) were applied to FGD gypsum to identify the Hg species in it. The FGD gypsum samples were collected from seven coal-fired power plants in China, with Hg concentrations ranging from 0.19 to 3.27μg/g. A series of pure Hg compounds were used as reference materials in TPD experiments and the results revealed that the decomposition temperatures of different Hg compounds increase in the order of Hg2Cl2

  15. Scale-dependent desorption of uranium from contaminated subsurface sediments

    NASA Astrophysics Data System (ADS)

    Liu, Chongxuan; Zachara, John M.; Qafoku, Nikolla P.; Wang, Zheming

    2008-08-01

    Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the U.S. Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor fine-grained (<2 mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter) and from its <2 mm U(VI)-associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multicomponent kinetic model that integrated a distributed rate of mass transfer with surface complexation reactions successfully described U(VI) release from the fine-grained U(VI)-associated materials. The field-textured sediment in the large column displayed dual-domain tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger nonequilibrium behavior than did PFBA and bromide and required a larger immobile porosity to describe. The dual-domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual-domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual-domain properties overpredicted effluent U(VI) concentrations, while the model based on tritium mass transfer underpredicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field-scale reactive transport models.

  16. Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation.

    PubMed

    Hu, Jing; Aitken, Michael D

    2012-10-01

    Dermal exposure can represent a significant health risk in settings involving potential contact with soil contaminated with polycyclic aromatic hydrocarbons (PAHs). However, there is limited work on the ability of PAHs in contaminated soil to reach the skin surface via desorption from the soil. We evaluated PAH desorption from a field-contaminated soil to a two-dimensional hydrophobic surface (C18 extraction disk) as a measure of potential dermal exposure as a function of soil loading (5-100 mg dry soil cm(-2)), temperature (20-40C), and soil moisture content (2-40%) over periods up to 16d. The efficacy of bioremediation in removing the most readily desorbable PAH fractions was also evaluated. Desorption kinetics were described well by an empirical two-compartment kinetic model. PAH mass desorbed to the C18 disk kept increasing at soil loadings well above the estimated monolayer coverage, suggesting mechanisms for PAH transport to the surface other than by direct contact. Such mechanisms were reinforced by observations that desorption occurred even with dry or moist glass microfiber filters placed between the C18 disk and the soil. Desorption of all PAHs was substantially reduced at a soil moisture content corresponding to field capacity, suggesting that transport through pore air contributed to PAH transport to the C18 disk. The lower molecular weight PAHs had greater potential to desorb from soil than higher molecular weight PAHs. Biological treatment of the soil in a slurry-phase bioreactor completely eliminated PAH desorption to the C18 disks. PMID:22704210

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

    NASA Astrophysics Data System (ADS)

    Shimada, Masashi; Hara, Masanori; Otsuka, Teppei; Oya, Yasuhisa; Hatano, Yuji

    2015-08-01

    Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 1026 m-2) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min-1 up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h.

  18. Initial stages of organic film growth characterized by thermal desorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Winkler, Adolf

    2016-01-01

    In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene-hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule-substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature.

  19. Conformational reduction of DOPA in the gas phase studied by laser desorption supersonic jet laser spectroscopy.

    PubMed

    Ishiuchi, Shun-ichi; Mitsuda, Haruhiko; Asakawa, Toshiro; Miyazaki, Mitsuhiko; Fujii, Masaaki

    2011-05-01

    The conformational reduction in catecholamine neurotransmitters was studied by resonance enhanced multi photon ionization (REMPI), ultraviolet-ultraviolet (UV-UV) hole burning and infrared (IR) dip spectroscopy with applying a laser desorption supersonic jet technique to DOPA, which is one of the catecholamine neurotransmitters and has one more phenolic OH group than tyrosine. It is concluded that DOPA has a single observable conformer in the gas phase at low temperature. Quantum chemical calculations at several levels with or without the dispersion correction were also carried out to study stable conformations. From the comparison between the computational IR spectra and the experimental ones, the most stable structure was determined. It is strongly suggested that the conformational reduction is caused by electrostatic interactions, such as a dipole-dipole interaction, between the chain and OH groups. PMID:21445451

  20. Initial stages of organic film growth characterized by thermal desorption spectroscopy

    PubMed Central

    Winkler, Adolf

    2015-01-01

    In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene-hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule-substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature. PMID:26778860